Polyisocyanate composition, polyurethane resin, two-component curable polyurethane composition, and coating material

ABSTRACT

A polyisocyanate composition contains a modified product of xylylene diisocyanate and a modified product of pentamethylene diisocyanate, and/or a modified product of the xylylene diisocyanate and the pentamethylene diisocyanate. The ratio of the pentamethylene diisocyanate with respect to the total amount of the xylylene diisocyanate and the pentamethylene diisocyanate is 60 mol % or more and 95 mol % or less.

TECHNICAL FIELD

The present invention relates to a polyisocyanate composition, apolyurethane resin obtained from the polyisocyanate composition, atwo-component curable polyurethane composition containing apolyisocyanate component containing the polyisocyanate composition, anda coating material obtained from the two-component curable polyurethanecomposition.

BACKGROUND ART

A polyurethane resin is usually produced by reaction of polyisocyanatewith an active hydrogen group-containing compound, and is, for example,widely used in various industrial fields such as coating materials,coatings, adhesive materials, pressure-sensitive adhesive materials, andelastomers.

As the polyisocyanate used in the production of the polyurethane resin,for example, xylylene diisocyanate and a derivative thereof, andhexamethylene diisocyanate and a derivative thereof are known. It isalso known to use a mixture of them.

The polyisocyanate is, for example, used as curing agents for coatingsand adhesives. To be specific, for example, a curing agent containing apolyol modified product of xylylene diisocyanate of 30 to 90 weight %,and a biuret modified product and/or a trimer of hexamethylenediisocyanate of 10 to 70 weight % is proposed (ref: for example, PatentDocument 1).

According to the curing agent, a two-component curable polyurethanecomposition having excellent adhesion properties, acid resistance/alkaliresistance, solvent resistance, contamination resistance, and weatherresistance can be obtained.

CITATION LIST Patent Document

-   Patent Document 1: Japanese Unexamined Patent Publication No.    2010-24386

SUMMARY OF THE INVENTION Problem to be Solved by the Invention

Meanwhile, in the field of the polyurethane resin, further improvementof the weather resistance may be demanded in accordance with its usages.

As the polyurethane resin, furthermore, chemical resistance andmechanical properties (hardness or the like), and moreover, designproperties such as smoothness may be demanded.

An object of the present invention is to provide a polyisocyanatecomposition capable of obtaining a polyurethane resin having excellentmechanical properties, design properties, and durability; a polyurethaneresin obtained from the polyisocyanate composition; a two-componentcurable polyurethane composition containing a polyisocyanate componentcontaining the polyisocyanate composition; and a coating materialobtained from the two-component curable polyurethane composition.

Means for Solving the Problem

The present invention [1] includes a polyisocyanate compositioncontaining a modified product of xylylene diisocyanate and a modifiedproduct of pentamethylene diisocyanate, and/or a modified product of thexylylene diisocyanate and the pentamethylene diisocyanate, and the ratioof the pentamethylene diisocyanate with respect to the total amount ofthe xylylene diisocyanate and the pentamethylene diisocyanate is 60 mol% or more and 95 mol % or less.

The present invention [2] includes the polyisocyanate compositiondescribed in the above-described [1], wherein the modified product is amultiple molecular product containing two or more molecules of thexylylene diisocyanate and/or the pentamethylene diisocyanate, and thecontent ratio of the multiple molecular product of four or moremolecules in the polyisocyanate composition is 30 mass % or more and 65mass % or less.

The present invention [3] includes the polyisocyanate compositiondescribed in the above-described [2], wherein the multiple molecularproduct of four or more molecules contains a multiple molecular productof four or more molecules of the xylylene diisocyanate at a ratio of 5mass % or more and 45 mass % or less.

The present invention [4] includes the polyisocyanate compositiondescribed in any one of the above-described [1] to [3], wherein themodified product contains at least one functional group selected fromthe group consisting of the following (a) to (i):

-   -   (a) isocyanurate group,    -   (b) allophanate group,    -   (c) biuret group,    -   (d) urethane group,    -   (e) urea group,    -   (f) uretdione group,    -   (g) iminooxadiazinedione group,    -   (h) uretonimine group, and    -   (i) carbodiimide group

The present invention [5] includes a polyurethane resin obtained fromreaction of the polyisocyanate composition described in any one of theabove-described [1] to [4] with an active hydrogen group-containingcompound.

The present invention [6] includes a two-component curable polyurethanecomposition containing a polyisocyanate component containing thepolyisocyanate composition described in any one of the above-described[1] to [4], and a polyol component.

The present invention [7] includes a coating material obtained from thetwo-component curable polyurethane composition described in theabove-described [6].

Effect of the Invention

According to the polyisocyanate composition of the present invention,the polyurethane resin having excellent mechanical properties (hardnessor the like), design properties, and durability (chemical resistance,weather resistance, or the like) can be obtained.

Also, the polyurethane resin, the two-component curable polyurethanecomposition, and the coating material of the present invention haveexcellent mechanical properties (hardness or the like), designproperties, and durability (chemical resistance, weather resistance, orthe like).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a graph illustrating a relationship of the mole ratio ofthe pentamethylene diisocyanate modified product with AE.

DESCRIPTION OF EMBODIMENTS

A polyisocyanate composition of the present invention contains amodified product of xylylene diisocyanate and a modified product ofpentamethylene diisocyanate, and/or a modified product of the xylylenediisocyanate and the pentamethylene diisocyanate.

That is, the polyisocyanate composition of the present inventionconsists of (1) a modified product of xylylene diisocyanate and amodified product of pentamethylene diisocyanate; (2) only a modifiedproduct of xylylene diisocyanate and pentamethylene diisocyanate; or (3)a modified product of xylylene diisocyanate and/or a modified product ofpentamethylene diisocyanate, and a modified product of xylylenediisocyanate and pentamethylene diisocyanate.

The polyisocyanate composition consisting of (1) the modified product ofthe xylylene diisocyanate and the modified product of the pentamethylenediisocyanate is described in detail.

The modified product of the xylylene diisocyanate is a multiplemolecular product containing two or more molecules of the xylylenediisocyanate, and can be obtained by modifying the xylylene diisocyanateby a method in accordance with a functional group to be described later.

In the xylylene diisocyanate, 1,2-xylylene diisocyanate (o-xylylenediisocyanate (o-XDI)), 1,3-xylylene diisocyanate (m-xylylenediisocyanate (m-XDI)), and 1,4-xylylene diisocyanate (p-xylylenediisocyanate (p-XDI)) are used as a structural isomer.

These xylylene diisocyanates can be used alone or in combination of twoor more. As the xylylene diisocyanate, preferably, 1,3-xylylenediisocyanate and 1,4-xylylene diisocyanate are used, more preferably,1,3-xylylene diisocyante is used.

The modified product of the xylylene diisocyante preferably contains atleast one functional group selected from the group consisting of thefollowing (a) to (i): (a) isocyanurate group. (b) allophanate group, (c)biuret group, (d) urethane group, (e) urea group. (f) uretdione group.(g) iminooxadiazinedione group, (h) uretonimine group, and (i)carbodiimide group.

The modified product containing the functional group (isocyanurategroup) of the above-described (a) is a trimer of the xylylenediisocyanate, and can be, for example, obtained by allowing the xylylenediisocyanate to react under the presence of a knownisocyanurate-formation catalyst to be trimerized.

The modified product containing the functional group (allophanate group)of the above-described (b) is an allophanate modified product of thexylylene diisocyanate, and can be, for example, obtained by allowing thexylylene diisocyanate to react with alcohols (described later) to thenfurther react under the presence of a known allophanate-formationcatalyst.

The modified product containing the functional group (biuret group) ofthe above-described (c) is a biuret modified product of the xylylenediisocyanate, and can be, for example, obtained by allowing the xylylenediisocyanate to react with water, tertiary alcohol (for example, t-butylalcohol or the like), and a secondary amine (for example, dimethylamine,diethylamine, or the like).

The polyisocyanate composition containing the functional group (urethanegroup) of the above-described (d) is a polyol modified product (polyolderivative) of the xylylene diisocyanate, and can be, for example,obtained by reaction of the xylylene diisocyanate with a polyolcomponent (for example, trihydric alcohols (described later) such astrimethylolpropane).

The modified product containing the functional group (urea group) of theabove-described (e) is a polyamine modified product of the xylylenediisocyanate, and can be, for example, obtained by reaction of thexylylene diisocyanate with water, a polyamine component, or the like.

The modified product containing the functional group (uretdione group)of the above-described (f) is a uretdione modified product (dimer) ofthe xylylene diisocyanate, and can be, for example, obtained by allowingthe xylylene diisocyanate to react under the presence of a knowndimerization-formation catalyst to be dimerized.

The modified product containing the functional group(iminooxadiazinedione group) of the above-described (g) is a trimer ofthe xylylene diisocyanate, and can be, for example, obtained by allowingthe xylylene diisocyanate to react under the presence of a knowniminooxadiazinedione-formation catalyst to be trimerized.

The modified product containing the functional group (uretonimine group)of the above-described (h) is a uretonimine modified product of thexylylene diisocyanate, and can be, for example, obtained by reaction ofthe xylylene diisocyanate with a carbodiimide compound.

The modified product containing the functional group (carbodiimidegroup) of the above-described (i) is a carbodiimide modified product ofthe xylylene diisocyanate, and can be, for example, obtained bydecarboxylation condensation reaction of the xylylene diisocyanate.

The modified product of the xylylene diisocyanate may contain at leastone of the functional group of the above-described (a) to (i), and canalso contain two or more functional groups. The modified product isproduced by appropriately using the above-described reactions incombination.

As the modified product of the xylylene diisocyanate, preferably, atrimer of the xylylene diisocyanate and a polyol modified product(polyol derivative) of the xylylene diisocyanate are used, morepreferably, a trimer of the xylylene diisocyanate is used. In otherwords, the modified product of the xylylene diisocyanate preferablycontains the trimer of the xylylene diisocyanate, more preferablyconsists of the trimer of the xylylene diisocyanate.

When the trimer of the xylylene diisocyanate is used, a polyurethaneresin having excellent mechanical properties (hardness or the like) anddurability (chemical resistance, weather resistance, or the like) can beobtained.

The trimer of the xylylene diisocyanate contains a modified productcontaining the isocyanurate group of the above-described (a)(hereinafter, referred to as an isocyanurate derivative) and a modifiedproduct containing the iminooxadiazinedione group of the above-described(g) (hereinafter, referred to as an iminooxadiazinedione derivative).

The isocyanurate derivative and the iminooxadiazinedione derivative arein the relationship of structural isomers, and the isocyanuratederivative is a symmetrical trimer and the iminooxadiazinedionederivative is an asymmetrical trimer.

An iminooxadiazinedione derivative may be produced as a by-product atthe time of the production of the isocyanurate derivative, and anisocyanurate derivative may be produced as a by-product at the time ofthe production of the iminooxadiazinedione derivative.

As described above, the isocyanurate derivative of the xylylenediisocyanate is obtained by subjecting the xylylene diisocyanate toisocyanurate-formation reaction under the presence of anisocyanurate-formation catalyst.

In the present invention, the isocyanurate-formation catalyst is notparticularly limited as long as the catalyst activates theisocyanurate-formation reaction. Examples thereof include tertiaryamines such as triethylamine, tributylamine, triethylenediamine, andsecondary amine copolymer (for example, polycondensate of secondaryamine such as dialkylamine, and a monomer copolymerizable with thesecondary amine (for example, phenol, formaldehyde, or the like));Mannich bases such as 2-dimethylaminomethylphenol and2,4,6-tris(dimethylaminomethyl) phenol; hydroxides of tetraalkylammoniumsuch as tetramethylammonium, tetraethylammonium, tetrabutylammonium,trimethylbenzylammonium, and tributylbenzylammonium or their organicsalt of weak acid; hydroxides of trialkylhydroxyalkylammonium such astrimethylhydroxypropylammonium (also known as:N-(2-hydroxypropyl)-N,N,N-trimethylammonium),trimethylhydroxyethylammonium, triethylhydroxypropylammonium, andtriethylhydroxyethylammonium or their organic salt of weak acid; metalsalts (for example, alkali metal salt, magnesium salt, tin salt, zincsalt, lead salt, or the like) of alkylcarboxylic acid such as aceticacid, caproic acid, octylic acid, myristic acid, and naphthenic acid;metal chelate compounds of β-diketone such as aluminumacetylacetone andlithiumacetylacetone; Friedel-Crafts catalysts such as aluminum chlorideand boron trifluoride; various organic metal compounds such astitaniumtetrabutyrate and tributylantimonyoxide; aminosilylgroup-containing compounds such as hexamethylsilazane; andhalogen-substituted organic phosphorus compounds such as hydrogendifluoride tetrabutylphosphonium.

These isocyanurate-formation catalysts can be used alone or incombination of two or more.

As the isocyanurate-formation catalyst, preferably, hydroxides oftetraalkylammonium and hydroxides of trialkylhydroxyalkylammonium areused, more preferably, hydroxides of tetraalkylammonium are used,further more preferably, hydroxides of trimethylbenzylammonium andhydroxides of tetrabutylammonium are used.

When the above-described catalyst is used as the isocyanurate-formationcatalyst, the xylylene diisocyanate can be subjected toisocyanurate-formation reaction at a particularly excellent reactionrate, thereby achieving excellent production efficiency.

The isocyanurate-formation catalyst may be used as a solid content of100%, or may be diluted in an organic solvent such as alcohol (forexample, methanol, isopropyl alcohol, isobutyl alcohol, ethylene glycol,or the like) at an appropriate ratio.

The mixing ratio (solid content) of the isocyanurate-formation catalystwith respect to 100 parts by mass of the xylylene diisocyanate is, forexample, 0.001 parts by mass (phr) or more, preferably 0.01 parts bymass (phr) or more, and for example, 0.1 parts by mass (phr) or less,preferably 0.05 parts by mass (phr) or less.

In the method, the isocyanurate-formation catalyst is blended into thexylylene diisocyanate at the above-described mixing ratio to be thenheated, so that it is subjected to the isocyanurate-formation reaction.

The reaction conditions of the isocyanurate-formation reaction of thexylylene diisocyanate are as follows: for example, under an inert gasatmosphere such as nitrogen gas under a normal pressure (atmosphericpressure), the reaction temperature (maximum achieving temperature) is,for example, 40° C. or more, preferably 60° C. or more, and for example,90° C. or less, preferably 80° C. or less, and the reaction time is, forexample, 30 minutes or more, preferably 60 minutes or more, and forexample, 600 minutes or less, preferably 480 minutes or less.

In the above-described reaction, for example, an organic phosphite orthe like described in Japanese Unexamined Patent Publication No.S61-129173 can be also blended as an auxiliary catalyst in order toadjust the isocyanurate-formation reaction.

Examples of the organic phosphite include an aliphatic organic phosphiteand an aromatic organic phosphite.

Examples of the aliphatic organic phosphite include alkyl monophosphitessuch as triethyl phosphite, tributyl phosphite, tris(2-ethylhexyl)phosphite, tridecyl phosphite, trilauryl phosphite, tris(tridecyl)phosphite, and tristearyl phosphite; di-, tri-, or tetra-phosphitesderived from aliphatic polyhydric alcohol such asdistearyl.pentaerythrityl.diphosphite,didodecyl.pentaerythritol.diphosphite,ditridecyl.pentaerythritol.diphosphite, andtripentaerythritol.triphosphite; furthermore, alicyclic polyphosphitessuch as hydrogenated bisphenol A phosphite polymer (molecular weight of2400 to 3000); and tris(2,3-dichloropropyl) phosphites.

Examples of the aromatic organic phosphite include aryl monophosphitessuch as triphenylphosphite, tris(nonylphenyl) phosphite,tris(2,4-di-t-butylphenyl) phosphite, diphenyldecylphosphite, anddiphenyl(tridecyl) phosphite; di-, tri-, or tetra-phosphites derivedfrom aromatic polyhydric alcohol such asdinonylpheyl.pentaerythritol.diphosphite,tetraphenyl.tetratridecyl.pentaerythrityl.tetraphosphite, andtetraphenyl.dipropyleneglycol.diphosphite; and furthermore, diphosphitesderived from bisphenol compounds such as dialkyl.bisphenol A.diphosphitehaving 1 to 20 carbon atoms and4,4′-butylidene-bis(3-methyl-6-t-butylphenyl-ditridecyl) phosphite.

These organic phosphites can be used alone or in combination of two ormore.

As the organic phosphite, preferably, an aromatic organic phosphite isused, more preferably, a di-, tri-, or tetra-phosphite derived fromaromatic polyhydric alcohol is used, further more preferably,tetraphenyl dipropyleneglycol diphosphite is used.

The mixing ratio of the organic phosphite with respect to 100 parts bymass of the xylylene diisocyanate is, for example, 0.001 parts by mass(phr) or more, preferably 0.005 parts by mass (phr) or more, and forexample, 0.05 parts by mass (phr) or less, preferably 0.03 parts by mass(phr) or less.

By blending the above-described organic phosphite at the above-describedratio as an auxiliary catalyst, improvement of the reaction speed andthe reaction rate can be achieved, and the gelation can be suppressed.

In the above-described reaction, a stabilizer such as hindered phenolantioxidant including 2,6-di(tert-butyl)-4-methylphenol (also known as:dibutylhydroxytoluene, hereinafter, may be abbreviated as BHT), andIRGANOX 1010. IRGANOX 1076, IRGANOX 1135, and IRGANOX 245 (hereinabove,manufactured by Ciba Japan KK, trade name) can be also added.

The mixing ratio of the stabilizer with respect to 100 parts by mass ofthe xylylene diisocyanate is, for example, 0.01 parts by mass (phr) ormore, preferably 0.02 parts by mass (phr) or more, and for example, 0.05parts by mass (phr) or less, preferably 0.03 parts by mass (phr) orless.

In the above-described reaction, a known reaction solvent may be blendedas needed, and furthermore, a known catalyst deactivator (for example,phosphoric acid, monochloroacetic acid, dodecylbenzenesulfonic acid,paratoluenesulfonic acid, ortho-toluene sulfonic acid, benzoyl chloride,p-toluenesulfonamide, o-toluenesulfonamide, or the like) can be alsoadded at an arbitrary timing.

After the completion of the reaction, the unreacted xylylenediisocyanate can be removed by a known method as needed.

To be specific, after the completion of the above-describedisocyanurate-formation reaction, the unreacted xylylene diisocyanatemonomer can be removed from an obtained reaction mixture of theisocyanurate derivative of the xylylene diisocyanate and the xylylenediisocyanate monomer by, for example, a known method such asdistillation such as thin-film distillation (Smith distillation) andextraction.

In the present invention, when the thin-film distillation is performedafter the completion of the isocyanurate-formation reaction of thexylylene diisocyanate, the yield (distillation yield) of theisocyanurate derivative obtained by the thin-film distillation is themass of the isocyanurate derivative of the xylylene diisocyanate withrespect to the mass of the reaction mixture, and is, for example, 15mass % or more, preferably 25 mass % or more, more preferably 40 mass %or more, and for example, 70 mass % or less, preferably 65 mass % orless, more preferably 60 mass % or less.

The distillation yield of the isocyanurate derivative of the xylylenediisocyanate can be obtained in conformity with Examples to be describedlater by calculating the ratio of the mass of the isocyanuratederivative of the xylylene diisocyanate with respect to the mass of thereaction mixture.

In the above-described reaction, alcohols can be also blended as needed.That is, the isocyanurate derivative can be modified with the alcohols.

Examples of the alcohols include aliphatic alcohols and aromaticalcohols. Preferably, aliphatic alcohols are used.

Examples of the aliphatic alcohols include monohydric aliphaticalcohols, dihydric aliphatic alcohols, trihydric aliphatic alcohols, andtetrahydric or more aliphatic alcohols.

Examples of the monohydric aliphatic alcohols include straight-chainmonohydric aliphatic alcohols and branched monohydric aliphaticalcohols.

Examples of the straight-chain monohydric aliphatic alcohols includemethanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol,n-heptanol, n-octanol, n-nonanol, n-decanol, n-undecanol, n-dodecanol(lauryl alcohol), n-tridecanol, n-tetradecanol, n-pentadecanol,n-hexadecanol, n-heptadecanol, n-octadecanol (stearyl alcohol),n-nonadecanol, and eicosanol.

Examples of the branched monohydric aliphatic alcohols includeisopropanol (also known as: isopropyl alcohol, IPA), isobutanol (alsoknown as: isobutyl alcohol, IBA), sec-butanol, tert-butanol,isopentanol, isohexanol, isoheptanol, isooctanol, 2-ethylhexanol (alsoknown as: 2-ethylhexyl alcohol, 2-EHA), isononanol, isodecanol,5-ethyl-2-nonanol, trimethylhonil alcohol, 2-hexyldecanol,3,9-diethyl-6-tridecanol, 2-isoheptylisoundecanol, 2-octyldodecanol, andanother branched alkanol (C (number of carbon atoms, hereinafter, thesame) 5 to 20).

Examples of the dihydric aliphatic alcohols include straight-chaindihydric aliphatic alcohols such as ethylene glycol, 1,3-propanediol(1,3-PG), 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol,1,4-dihydroxy-2-butene, diethylene glycol, triethylene glycol,dipropylene glycol, and another straight-chain alkane (C7 to 20) diol;branched dihydric aliphatic alcohols such as 1,2-propanediol,1,3-butylene glycol (also known as: 1,3-butanediol), 1,2-butyleneglycol, neopentyl glycol, 3-methyl-1,5-pentanediol (MPD),2,2,4-trimethyl-1,3-pentanediol (TMPD), 3,3-dimethylolheptane,2,6-dimethyl-1-octene-3,8-diol, and another branched alkane (C7 to 20)diol; and alicyclic dihydric aliphatic alcohols such as 1,3- or1,4-cyclohexanedimethanol and a mixture thereof, 1,3- or1,4-cyclohexanediol and a mixture thereof, and hydrogenated bisphenol A.

Examples of the trihydric aliphatic alcohols include glycerin andtrimethylolpropane.

Examples of the tetrahydric or more aliphatic alcohols includetetramethylolmethane, D-sorbitol, xylitol, and D-mannitol.

When the alcohols have one or more hydroxy group in a molecule, themolecular structure other than that is not particularly limited as longas excellent effect of the present invention is not inhibited, and forexample, the alcohols can have an ester group, an ether group, acyclohexane ring, and an aromatic ring in its molecule. Examples of thealcohols include an ether group-containing monohydric alcohol which isan addition polymer (random and/or block polymer of two or more alkyleneoxides) of the above-described monohydric alcohol and the alkylene oxide(for example, ethylene oxide, propylene oxide, or the like), and anester group-containing monohydric alcohol which is an addition polymerof the above-described monohydric alcohol and lactone (for example,ε-caprolactone, δ-valerolactone, or the like).

These alcohols can be used alone or in combination of two or more.

As the alcohols, preferably, aliphatic alcohols are used, morepreferably, monohydric and dihydric aliphatic alcohols are used, furthermore preferably, dihydric aliphatic alcohols are used.

As the aliphatic alcohols, preferably, aliphatic alcohols having 1 to 20carbon atoms are used, more preferably, aliphatic alcohols having 2 to20 carbon atoms are used, further more preferably, aliphatic alcoholshaving 2 to 8 carbon atoms are used.

As the aliphatic alcohols, preferably, branched monohydric and dihydricaliphatic alcohols are used, more preferably, branched dihydricaliphatic alcohols are used, particularly preferably, 1,3-butanediol isused.

The alcohols are blended so that the average functionality is two ormore in the isocyanurate derivative of the xylylene diisocyanate, andthe mixing ratio thereof with respect to 100 parts by mass of thexylylene diisocyanate is, for example, 0.1 parts by mass or more,preferably 1.0 part by mass or more, more preferably 1.5 parts by massor more, and for example, 10 parts by mass or less, preferably 5.0 partsby mass or less.

In the reaction, the xylylene diisocyanate and the alcohols are blendedso that the equivalent ratio (NCO/OH) of the isocyanate group of thexylylene diisocyanate with respect to the hydroxy group of the alcoholsis, for example, 5 or more, preferably 10 or more, more preferably 20 ormore, and usually 1000 or less, preferably 100 or less, more preferably50 or less.

Examples of the method for modifying the isocyanurate derivative of thexylylene diisocyanate with the alcohols include a method in which first,the xylylene diisocyanate is allowed to react with the alcohols; next,the isocyanurate-formation reaction is performed under the presence ofthe isocyanurate catalyst; and thereafter, the unreacted xylylenediisocyanate is removed and a method in which first, only the xylylenediisocyanate is subjected to isocyanurate-formation reaction by theabove-described method; then, the unreacted xylylene diisocyanate isremoved; and thereafter, the obtained polyisocyanurate is allowed toreact with the alcohols.

Preferably, first, the xylylene diisocyanate is allowed to react withthe alcohols; next, the isocyanurate-formation reaction is performedunder the presence of the isocyanurate-formation catalyst; andthereafter, the unreacted xylylene diisocyanate is removed.

To be specific, in this method, first, the xylylene diisocyanate ismixed with the alcohols to react.

The reaction of the xylylene diisocyanate with the alcohols is theurethane-formation reaction (including allophanate-formation reaction),and the reaction conditions are as follows: for example, under an inertgas atmosphere such as nitrogen gas under a normal pressure (atmosphericpressure), the reaction temperature is, for example, room temperature(for example, 25° C.) or more, preferably 40° C. or more, and forexample, 100° C. or less, preferably 90° C. or less, and the reactiontime is, for example, 0.05 hours or more, preferably 0.2 hours or more,and for example, 10 hours or less, preferably 6 hours or less, morepreferably 3 hours or less.

In the above-described urethane-formation reaction, for example, a knownurethane-formation catalyst such as amines and an organic metal compoundmay be added as needed.

Examples of the amines include tertiary amines such as triethylamine,triethylenediamine, bis-(2-dimethylaminoethyl) ether, andN-methylmorpholine; quaternary ammonium salts such astetraethylhydroxylammonium; and imidazoles such as imidazole and2-ethyl-4-methylimidazole.

Examples of the organic metal compound include organic tin compoundssuch as tin acetate, tin octylate, tin oleate, tin laurate, dibutyltindiacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltindimercaptide, dibutyltin maleate, dibutyltin dilaurate (dibutyltin (IV)dilaurate), dibutyltin dineodecanoate, dioctyltin dimethylcaptide,dioctyltin dilaurate, and dibutyltin dichloride; organic lead compoundssuch as lead octanoate and lead naphthenate; organic nickel compoundssuch as nickel naphthenate; organic cobalt compounds such as cobaltnaphthenate; organic copper compounds such as copper octenoate; andorganic bismuth compounds such as bismuth octylate and bismuthneodecanoate.

Furthermore, examples of the urethane-formation catalyst includepotassium salts such as potassium carbonate, potassium acetate, andpotassium octylate.

These urethane-formation catalysts can be used alone or in combinationof two or more.

In the method, the isocyanurate-formation catalyst is blended into thereaction liquid to be obtained at the above-described mixing ratio, andthe reaction product of the xylylene diisocyanate and the alcohols issubjected to isocyanurate-formation reaction. The reaction conditions inthe isocyanurate-formation reaction are the same as those describedabove. After the completion of the reaction, the unreacted xylylenediisocyanate is removed by a known removing method such as distillationas needed.

In this manner, the isocyanurate derivative of the xylylene diisocyanatethat is modified with the alcohols can be obtained.

For example, when the method in which only the xylylene diisocyanate issubjected to the isocyanurate-formation reaction; then, the unreactedxylylene diisocyanate is removed; and the obtained polyisocyanate isallowed to react with the alcohols (the latter method in the descriptionabove) is used, the isocyanurate derivative of the xylylene diisocyanatereacts with the alcohols. The reaction is the urethane-formationreaction, and the reaction is performed under the reaction conditions ofthe urethane-formation reaction described above.

In this manner, the isocyanurate derivative of the xylylene diisocyanatethat is modified with the alcohols can be also produced.

When the isocyanurate derivative of the xylylene diisocyanate ismodified with the alcohols, an allophanate derivative of the xylylenediisocyanate may be obtained as a by-product. In this case, theisocyanurate derivative of the xylylene diisocyanate contains theallophanate derivative of the xylylene diisocyanate as an auxiliarycomponent inevitably contained. In other words, when the isocyanuratederivative of the xylylene diisocyanate is modified with the alcohols,an isocyanurate composition containing the isocyanurate derivative ofthe xylylene diisocyanate and the allophanate derivative of the xylylenediisocyanate is obtained.

In the isocyanurate derivative of the xylylene diisocyanate that ismodified with the alcohols, the modification amount (alcoholmodification rate of the isocyanurate derivative) of the alcohols withrespect to the isocyanurate derivative is, for example, 0.5 mass % ormore, preferably 1.0 mass % or more, more preferably 3.0 mass/% or more,further more preferably 4.0 mass % or more, and for example, 15 mass %or less, preferably 10 mass % or less, more preferably 6.0 mass % orless.

The modification amount (alcohol modification rate) of the alcohols withrespect to the isocyanurate derivative can be calculated by thefollowing formula.Alcohol Modification Rate (mass %) of Isocyanurate Derivative=(AlcoholModification Rate (mass %) in Reaction Mixture/Distillation Yield (mass%))×100

The alcohol modification rate in the reaction mixture is themodification amount of the alcohols with respect to the xylylenediisocyanate and the isocyanurate derivative in the reaction mixture,and can be calculated as the mixing ratio of the charged mass of thealcohols with respect to the charged mass of the xylylene diisocyanate.

Generally, the alcohol modification rate can be also calculated by¹H-NMR measurement.

As the isocyanurate derivative of the xylylene diisocyanate, any one ofthe isocyanurate derivative of the xylylene diisocyanate that is notessentially modified with the alcohols and the isocyanurate derivativeof the xylylene diisocyanate that is modified with the alcohols may beused. Preferably, the isocyanurate derivative of the xylylenediisocyanate that is modified with the alcohols is used.

In the present invention, the isocyanurate derivative that is notessentially modified with the alcohols is defined as a derivative thatdoes not intentionally contain an active hydrogen group-containingcompound such as the above-described alcohols as a modifier. Forexample, at the time of the production of the isocyanurate derivative,it is allowed to contain a modified group (for example, urethane group,urea group, or the like) with respect to the isocyanurate derivativebased on the active hydrogen group-containing compound (for example,solvent of isocyanurate-formation catalyst (for example, methanol or thelike), water, or the like) inevitably mixed (hereinafter, the same).

The concentration of the isocyanate group (solid content of 100 mass %)of an isocyanurate-formation reaction liquid (before distillation) inthe isocyanurate derivative of the xylylene diisocyanate is, forexample, 5 mass % or more, preferably 10 mass % or more, more preferably15 mass % or more, and for example, 50 mass % or less, preferably 40mass % or less, more preferably 35 mass % or less.

The concentration of the isocyanate group (solid content of 100 mass %)in the isocyanurate derivative of the xylylene diisocyanate can beobtained in conformity with Examples to be described later.

In the isocyanurate derivative of the xylylene diisocyanate, theconcentration of the isocyanate monomer (concentration of the unreactedxylylene diisocyanate) is, for example, 2 mass % or less, preferably 1mass % or less, more preferably 0.5 mass % or less.

In the isocyanurate derivative of the xylylene diisocyanate, theconversion rate (reaction rate) of the isocyanate group is, for example,5 mass % or more, preferably 10 mass % or more, more preferably 15 mass% or more, and for example, 50 mass % or less, preferably 40 mass % orless, more preferably 35 mass % or less.

When the isocyanurate derivative of the xylylene diisocyanate is notessentially modified with the alcohols, the conversion rate (reactionrate) of the isocyanate group is substantially the same as theisocyanurate conversion rate (trimer conversion rate).

That is, the isocyanurate conversion rate (trimer conversion rate) is,for example, 5 mass % or more, preferably 10 mass % or more, morepreferably 15 mass % or more, and for example, 50 mass % or less,preferably 40 mass % or less, more preferably 35 mass % or less.

Meanwhile, when the isocyanurate derivative of the xylylene diisocyanateis modified with the alcohols, the conversion rate (reaction rate) ofthe isocyanate group is the total value of the urethane conversion ratewith the alcohols and the isocyanurate conversion rate (trimerconversion rate).

In this case, the urethane conversion rate is, for example, 1 mass % ormore, preferably 3 mass % or more, more preferably 5 mass % or more, andfor example, 30 mass % or less, preferably 20 mass % or less, morepreferably 10 mass % or less.

The isocyanurate conversion rate (trimer conversion rate) is, forexample, 5 mass % or more, preferably 10 mass % or more, more preferably15 mass % or more, and for example, 50 mass % or less, preferably 40mass % or less, more preferably 35 mass % or less.

The conversion rate of the isocyanate group of the xylylenediisocyanate, the urethane conversion rate, and the isocyanurateconversion rate can be obtained in conformity with Examples to bedescribed later by calculating the decreasing rate of the concentrationof the isocyanate group in the reaction liquid with respect to theconcentration of the isocyanate group of the xylylene diisocyanate atthe time of charging.

The modified product of the xylylene diisocyanate can contain a multiplemolecular product containing four or more molecules of the xylylenediisocyanate (hereinafter, referred to as four or more molecularproduct).

When the modified product of the xylylene diisocyanate is theisocyanurate derivative, for example, the four or more molecular productis a multiple molecular product that has a molecular weight of themolecular weight or more of a reaction product (four molecular product)of one molecule of the xylylene diisocyanate in addition to theisocyanurate one nuclide (to be specific, a compound in which threemolecules of the xylylene diisocyanate form one isocyanurate ring, thatis, three molecular product of the xylylene diisocyanate via theisocyanurate ring). To be specific, examples thereof include twonuclides (five molecular product), three nuclides (seven molecularproduct), and n nuclides ((2n+1) molecular product).

In the modified product of the xylylene diisocyanate, the content ratioof the four or more molecular product with respect to the total amountof the modified product of the xylylene diisocyanate is, for example, 20mass % or more, preferably 25 mass % or more, more preferably 30 mass %or more, further more preferably 33 mass % or more, particularlypreferably 35 mass % or more, and for example, 80 mass % or less,preferably 70 mass % or less, more preferably 65 mass % or less, furthermore preferably 60 mass % or less, particularly preferably 55 mass % orless.

In the modified product of the xylylene diisocyanate, the content ratioof the four or more molecular product can be calculated by measuring themolecular weight distribution of the modified product of the xylylenediisocyanate based on the calibration curve of the standard polyethyleneoxide with gel permeation chromatograph (GPC) equipped with a refractiveindex detector (RID), and as the peak area ratio (area ratio of the fouror more molecular product with respect to the area ratio of the modifiedproduct of the xylylene diisocyanate) in the obtained chromatogram(chart).

In the modified product of the xylylene diisocyanate, the area ratio ofthe four or more molecular product can be obtained as the area ratiocorresponding to the polyethylene oxide-based molecular weight of 600 ormore.

In the modified product of the xylylene diisocyanate, when the contentratio of the four or more molecular product is within theabove-described range, the polyurethane resin (described later) havingexcellent mechanical properties (hardness or the like), designproperties, and durability (chemical resistance, weather resistance, orthe like) can be obtained.

The modified product of the xylylene diisocyanate may containphosphorus, when the organic phosphite or the like is used as theauxiliary catalyst.

The concentration of the phosphorus of the modified product(composition) of the xylylene diisocyanate is, for example, 5 ppm ormore, preferably 10 ppm or more, and for example, 500 ppm or less,preferably 300 ppm or less.

The concentration of the phosphorus can be obtained in conformity withExamples to be described later.

The modified product of the pentamethylene diisocyanate is a multiplemolecular product containing two or more molecules of the pentamethylenediisocyanate, and can be obtained by modifying the pentamethylenediisocyanate by a method in accordance with the functional group to bedescribed later.

Examples of the pentamethylene diisocyanate include 1,5-pentamethylenediisocyanate, 1,4-pentamethylene diisocyanate, and 1,3-pentamethylenediisocyanate.

These pentamethylene diisocyanates can be used alone or in combinationof two or more.

As the pentamethylene diisocyanate, preferably, 1,5-pentamethylenediisocyanate is used.

The pentamethylene diisocyanate can be, for example, obtained as acommercially available product, and the pentamethylene diisocyanate canbe also produced as follows: pentamethylenediamine or the salt thereofis produced by a known method, for example, a biochemical method (forexample, decarboxylation enzyme reaction of lysin and/or salt thereof,or the like), and the pentamethylenediamine or the salt thereof issubjected to isocyanate-formation reaction by a method such asphosgenation method or carbamating method.

The pentamethylene diisocyanate is refined by a known method such asrefinement (distillation) and extraction as needed.

The purity of the pentamethylene diisocyanate is, for example, 95 mass %or more, preferably 98 mass % or more, more preferably 99 mass % ormore, further more preferably 99.5 mass % or more, particularlypreferably 99.9 mass % or more, and usually 100 mass % or less.

The concentration of the hydrolyzable chlorine (hereinafter, may beabbreviated as HC) of the pentamethylene diisocyanate is, for example,200 ppm or less, preferably 100 ppm or less, more preferably 80 ppm orless, further more preferably 70 ppm or less, and usually 1 ppm or more.

The modified product of the pentamethylene diisocyanate preferablycontains at least one functional group selected from the groupconsisting of the above-described (a) to (i) in the same manner as themodified product of the xylylene diisocyanate described above: (a)isocyanurate group, (b) allophanate group, (c) biuret group, (d)urethane group, (e) urea group, (f) uretdione group, (g)iminooxadiazinedione group, (h) uretonimine group, and (i) carbodiimidegroup.

The modified product containing the functional group (isocyanurategroup) of the above-described (a) is a trimer of the pentamethylenediisocyanate, and can be, for example, obtained by allowing thepentamethylene diisocyanate to react under the presence of a knownisocyanurate-formation catalyst to be trimerized.

The modified product containing the functional group (allophanate group)of the above-described (b) is an allophanate modified product of thepentamethylene diisocyanate, and can be, for example, obtained byallowing the pentamethylene diisocyanate to react with theabove-described alcohols to then further react under the presence of aknown allophanate-formation catalyst.

The modified product containing the functional group (biuret group) ofthe above-described (c) is a biuret modified product of thepentamethylene diisocyanate, and can be, for example, obtained byallowing the pentamethylene diisocyanate to react with water, tertiaryalcohol (for example, t-butyl alcohol or the like), and a secondaryamine (for example, dimethylamine, diethylamine, or the like).

The polyisocyanate composition containing the functional group (urethanegroup) of the above-described (d) is a polyol modified product (polyolderivative) of the pentamethylene diisocyanate, and can be, for example,obtained by reaction of the pentamethylene diisocyanate with a polyolcomponent (for example, the above-described trihydric alcohols such astrimethylolpropane).

The modified product containing the functional group (urea group) of theabove-described (e) is a polyamine modified product of thepentamethylene diisocyanate, and can be, for example, obtained byreaction of the pentamethylene diisocyanate with water, a polyaminecomponent, or the like.

The modified product containing the functional group (uretdione group)of the above-described (f) is a uretdione modified product (dimer) ofthe pentamethylene diisocyanate, and can be, for example, obtained byallowing the pentamethylene diisocyanate to react under the presence ofa known dimerization-formation catalyst to be dimerized.

The modified product containing the functional group(iminooxadiazinedione group) of the above-described (g) is a trimer ofthe pentamethylene diisocyanate, and can be, for example, obtained byallowing the pentamethylene diisocyanate to react under the presence ofa known iminooxadiazinedione-formation catalyst to be trimerized.

The modified product containing the functional group (uretonimine group)of the above-described (h) is a uretonimine modified product of thepentamethylene diisocyanate, and can be, for example, obtained byreaction of the pentamethylene diisocyanate with a carbodiimidecompound.

The modified product containing the functional group (carbodiimidegroup) of the above-described (i) is a carbodiimide modified product ofthe pentamethylene diisocyanate, and can be, for example, obtained bydecarboxylation condensation reaction of the pentamethylenediisocyanate.

The modified product of the pentamethylene diisocyanate may contain atleast one of the functional group of the above-described (a) to (i), andcan also contain two or more functional groups. The modified product isproduced by appropriately using the above-described reactions incombination.

As the modified product of the pentamethylene diisocyanate, preferably,a trimer of the pentamethylene diisocyanate is used. In other words, themodified product of the pentamethylene diisocyanate preferably containsthe trimer of the pentamethylene diisocyanate, more preferably consistsof the trimer of the pentamethylene diisocyanate.

When the trimer of the pentamethylene diisocyanate is used, apolyurethane resin having excellent mechanical properties (hardness orthe like) and durability (chemical resistance, weather resistance, orthe like) can be obtained.

The trimer of the pentamethylene diisocyanate contains a modifiedproduct containing the isocyanurate group of the above-described (a)(isocyanurate derivative) and a modified product containing theiminooxadiazinedione group of the above-described (g)(iminooxadiazinedione derivative).

The isocyanurate derivative and the iminooxadiazinedione derivative arein the relationship of structural isomers, and the isocyanuratederivative is a symmetrical trimer and the iminooxadiazinedionederivative is an asymmetrical trimer.

An iminooxadiazinedione derivative may be produced as a by-product atthe time of the production of the isocyanurate derivative, and anisocyanurate derivative may be produced as a by-product at the time ofthe production of the iminooxadiazinedione derivative.

As the trimer of the pentamethylene diisocyanate, preferably, anisocyanurate derivative is used.

The isocyanurate derivative of the pentamethylene diisocyanate is, forexample, obtained by subjecting the above-described pentamethylenediisocyanate to isocyanurate-formation reaction under the presence of anisocyanurate-formation catalyst.

As the isocyanurate-formation catalyst, the isocyanurate-formationcatalyst illustrated as the catalyst in the isocyanuration-formationreaction of the xylylene diisocyanate is used.

As the isocyanurate-formation catalyst, preferably, organic weak acidsalts of trialkylhydroxyalkylammonium are used, more preferably, organicweak acid salts of trimethylhydroxypropylammonium are used.

The mixing ratio (solid content) of the isocyanurate-formation catalystwith respect to 100 parts by mass of the pentamethylene diisocyanate is,for example, 0.001 parts by mass (phr) or more, preferably 0.005 partsby mass (phr) or more, more preferably 0.01 parts by mass (phr) or more,and for example, 0.1 parts by mass (phr) or less, preferably 0.05 partsby mass (phr) or less, more preferably 0.03 parts by mass (phr) or less.

The reaction conditions of the isocyanurate-formation reaction of thepentamethylene diisocyanate are as follows: for example, under an inertgas atmosphere such as nitrogen gas under a normal pressure (atmosphericpressure), the reaction temperature (maximum achieving temperature) is,for example, 40° C. or more, preferably 60° C. or more, and for example,120° C. or less, preferably 110° C. or less, more preferably 100° C. orless, and the reaction time is, for example, 5 minutes or more,preferably 10 minutes or more, and for example, 180 minutes or less,preferably 120 minutes or less, more preferably 90 minutes or less.

In the above-described reaction, the above-described organic phosphiteor the like can be also blended as an auxiliary catalyst in the samemanner as the isocyanurate-formation reaction of the xylylenediisocyanate described above.

As the organic phosphite, preferably, an aliphatic organic phosphite isused, more preferably, alkylmonophosphite is used, further morepreferably, tridecylphosphite is used.

The mixing ratio of the organic phosphite with respect to 100 parts bymass of the pentamethylene diisocyanate is, for example, 0.01 parts bymass (phr) or more, preferably 0.03 parts by mass (phr) or more, and forexample, 0.5 parts by mass (phr) or less, preferably 0.3 parts by mass(phr) or less.

The mixing ratio of the organic phosphite with respect to thepentamethylene diisocyanate is, for example, 200 ppm or more, preferably300 ppm or more, and for example, 5000 ppm or less, preferably 2000 ppmor less.

The addition amount of the organic phosphite with respect to chlorineconversion amount of the hydrolyzable chlorine in the pentamethylenediisocyanate is, for example, 0.4 equivalent or more, preferably 0.7equivalent or more, and for example, 2.5 equivalent or less, preferably1.5 equivalent or less.

By blending the above-described organic phosphite at the above-describedratio as an auxiliary catalyst, improvement of the reaction speed andthe reaction rate can be achieved, and the gelation can be suppressed.

In the above-described reaction, a stabilizer such as the hinderedphenol antioxidant described above can be also added in the same manneras the isocyanurate-formation reaction of the xylylene diisocyanate.

The mixing ratio of the stabilizer with respect to 100 parts by mass ofthe pentamethylene diisocyanate is, for example, 0.01 parts by mass(phr) or more, preferably 0.02 parts by mass (phr) or more, and forexample, 0.1 parts by mass (phr) or less, preferably 0.08 parts by mass(phr) or less.

In the above-described reaction, a known reaction solvent may be blendedas needed, and furthermore, a known catalyst deactivator (for example,phosphoric acid, monochloroacetic acid, dodecylbenzenesulfonic acid,paratoluenesulfonic acid, ortho-toluene sulfonic acid, benzoyl chloride,p-toluenesulfonamide, o-toluenesulfonamide, or the like) can be alsoadded at an arbitrary timing.

After the completion of the reaction, the unreacted pentamethylenediisocyanate can be removed by a known method as needed.

To be specific, after the completion of the above-described isocyanuratereaction, the unreacted pentamethylene diisocyanate monomer can beremoved from an obtained reaction mixture of the isocyanurate derivativeof the pentamethylene diisocyanate and the pentamethylene diisocyanatemonomer by, for example, a known method such as distillation such asthin-film distillation (Smith distillation) and extraction.

In the present invention, when the thin-film distillation is performedafter the completion of the isocyanurate-formation reaction of thepentamethylene diisocyanate, the yield (distillation yield) of theisocyanurate derivative obtained by the thin-film distillation is themass of the isocyanurate derivative of the pentamethylene diisocyanatewith respect to the mass of the reaction mixture, and is, for example, 5mass % or more, preferably 10 mass % or more, more preferably 15 mass %or more, and for example, 70 mass % or less, preferably 65 mass % orless, more preferably 60 mass % or less.

The distillation yield of the isocyanurate derivative of thepentamethylene diisocyanate can be obtained in conformity with Examplesto be described later by calculating the ratio of the mass of theisocyanurate derivative of the pentamethylene diisocyanate with respectto the mass of the reaction mixture.

In the above-described reaction, alcohols can be also blended as needed.That is, the isocyanurate derivative can be modified with the alcohols.

As the alcohols, the alcohols illustrated as the alcohols in theisocyanurate-formation reaction of the xylylene diisocyanate are used.

As the alcohols, preferably, aliphatic alcohols are used, morepreferably, monohydric to trihydric aliphatic alcohols are used, furthermore preferably, monohydric aliphatic alcohols are used.

As the aliphatic alcohols, preferably, aliphatic alcohols having 1 to 20carbon atoms are used, more preferably, aliphatic alcohols having 2 to20 carbon atoms are used, further more preferably, aliphatic alcoholshaving 2 to 8 carbon atoms are used.

As the aliphatic alcohols, preferably, branched monohydric aliphaticalcohols, dihydric aliphatic alcohols, and trihydric aliphatic alcoholsare used, more preferably, isobutanol (also known as: isobutyl alcohols,IBA), 1,3-butanediol, and trimethylolpropane are used, further morepreferably, isobutanol (also known as: isobutyl alcohols, IBA) is used.

The alcohols are blended so that the average functionality is two ormore in the isocyanurate derivative of the pentamethylene diisocyanate,and the mixing ratio thereof with respect to 100 parts by mass of thepentamethylene diisocyanate is, for example, 0.1 parts by mass or more,preferably 0.2 parts by mass or more, and for example, 10 parts by massor less, preferably 5.0 parts by mass or less, more preferably 1.0 partby mass or less.

In the reaction, the pentamethylene diisocyanate and the alcohols areblended so that the equivalent ratio (NCO/OH) of the isocyanate group ofthe pentamethylene diisocyanate with respect to the hydroxy group of thealcohols is, for example, 5 or more, preferably 10 or more, morepreferably 20 or more, and usually 1000 or less, preferably 600 or less,more preferably 500 or less.

Examples of the method for modifying the isocyanurate derivative of thepentamethylene diisocyanate with the alcohols include a method in whichfirst, the pentamethylene diisocyanate is allowed to react with thealcohols; next, the isocyanurate-formation reaction is performed underthe presence of the isocyanurate-formation catalyst; and thereafter, theunreacted pentamethylene diisocyanate is removed in the same manner asthe isocyanurate-formation reaction of the xylylene diisocyanatedescribed above and a method in which first, only the pentamethylenediisocyanate is subjected to isocyanurate-formation reaction by theabove-described method; then, the unreacted pentamethylene diisocyanateis removed; and thereafter, the obtained polyisocyanurate is allowed toreact with the alcohols.

Preferably, first, the pentamethylene diisocyanate is allowed to reactwith the alcohols; next, the isocyanurate-formation reaction isperformed under the presence of the isocyanurate-formation catalyst; andthereafter, the unreacted pentamethylene diisocyanate is removed.

The reaction of the pentamethylene diisocyanate with the alcohols is theurethane-formation reaction (including allophanate-formation reaction),and the reaction conditions are as follows: for example, under an inertgas atmosphere such as nitrogen gas under a normal pressure (atmosphericpressure), the reaction temperature is, for example, room temperature(for example, 25° C.) or more, preferably 40° C. or more, and forexample, 100° C. or less, and the reaction time is, for example, 0.05hours or more, preferably 0.2 hours or more, and for example, 10 hoursor less, preferably 4 hours or less.

In the above-described urethane-formation reaction, for example, theabove-described urethane-formation catalyst such as amines and anorganic metal compound may be added as needed.

In the method, the isocyanurate-formation catalyst is blended into thereaction liquid to be obtained at the above-described mixing ratio, andthe reaction product of the pentamethylene diisocyanate and the alcoholsis subjected to isocyanurate-formation reaction. The reaction conditionsin the isocyanurate-formation reaction are the same as those describedabove. After the completion of the reaction, the unreactedpentamethylene diisocyanate is removed by a known removing method suchas distillation as needed.

In this manner, the isocyanurate derivative of the pentamethylenediisocyanate that is modified with the alcohols can be obtained.

For example, when the method in which only the pentamethylenediisocyanate is subjected to the isocyanurate-formation reaction; then,the unreacted pentamethylene diisocyanate is removed; and the obtainedpolyisocyanate is allowed to react with the alcohols (the latter methodin the description above) is used, the isocyanurate derivative of thepentamethylene diisocyanate reacts with the alcohols. The reaction isthe urethane-formation reaction, and the reaction is performed under thereaction conditions of the urethane-formation reaction described above.

In this manner, the isocyanurate derivative of the pentamethylenediisocyanate that is modified with the alcohols can be also produced.

When the isocyanurate derivative of the pentamethylene diisocyanate ismodified with the alcohols, an allophanate derivative of thepentamethylene diisocyanate may be obtained as a by-product. In thiscase, the isocyanurate derivative of the pentamethylene diisocyanatecontains the allophanate derivative of the pentamethylene diisocyanateas an auxiliary component inevitably contained. In other words, when theisocyanurate derivative of the pentamethylene diisocyanate is modifiedwith the alcohols, an isocyanurate composition containing theisocyanurate derivative of the pentamethylene diisocyanate and theallophanate derivative of the pentamethylene diisocyanate is obtained.

In the isocyanurate derivative of the pentamethylene diisocyanate thatis modified with the alcohols, the modification amount (alcoholmodification rate of the isocyanurate derivative) of the alcohols withrespect to the isocyanurate derivative is, for example, 0.01 mass % ormore, preferably 0.1 mass % or more, more preferably 1.0 mass % or more,and for example, 35 mass % or less, preferably 30 mass % or less, morepreferably 25 mass % or less, further more preferably 20 mass % or less.

In the isocyanurate derivative of the pentamethylene diisocyanate, whenthe alcohol modification rate is within the above-described range, thepolyurethane resin (described later) having excellent mechanicalproperties (hardness or the like), design properties, and durability(chemical resistance, weather resistance, or the like) can be obtained.

The modification amount (alcohol modification rate) of the alcohols withrespect to the isocyanurate derivative can be obtained by the samecalculation formula as that of the alcohol modification rate in theisocyanurate derivative of the xylylene diisocyanate described above.

In the same manner as the description above, the alcohol modificationrate can be also calculated by ¹H-NMR measurement.

As the isocyanurate derivative of the pentamethylene diisocyanate, anyone of the isocyanurate derivative of the pentamethylene diisocyanatethat is not essentially modified with the alcohols and the isocyanuratederivative of the pentamethylene diisocyanate that is modified with thealcohols may be used. Preferably, the isocyanurate derivative of thepentamethylene diisocyanate that is modified with the alcohols is used.

The concentration of the isocyanate group (solid content of 100 mass %)in the isocyanurate derivative of the pentamethylene diisocyanate is,for example, 10 mass % or more, preferably 15 mass % or more, morepreferably 22 mass % or more, and for example, 30 mass % or less,preferably 26 mass % or less.

The concentration of the isocyanate group (solid content of 100 mass %)in the isocyanurate derivative of the pentamethylene diisocyanate can beobtained in conformity with Examples to be described later.

In the isocyanurate derivative of the pentamethylene diisocyanate, theconcentration of the isocyanate monomer (concentration of the unreactedpentamethylene diisocyanate) is, for example, 2 mass % or less,preferably 1 mass % or less, more preferably 0.5 mass % or less.

In the isocyanurate derivative of the pentamethylene diisocyanate, theconversion rate (reaction rate) of the isocyanate group is, for example,5 mass % or more, preferably 7 mass % or more, more preferably 10 mass %or more, and for example, 40 mass % or less, preferably 35 mass % orless, more preferably 30 mass % or less.

When the isocyanurate derivative of the pentamethylene diisocyanate isnot essentially modified with the alcohols, the conversion rate(reaction rate) of the isocyanate group is substantially the same as theisocyanurate conversion rate (trimer conversion rate).

That is, the isocyanurate conversion rate (trimer conversion rate) is,for example, 5 mass % or more, preferably 7 mass % or more, morepreferably 10 mass % or more, and for example, 40 mass % or less,preferably 35 mass % or less, more preferably 30 mass % or less.

Meanwhile, when the isocyanurate derivative of the pentamethylenediisocyanate is modified with the alcohols, the conversion rate(reaction rate) of the isocyanate group is the total value of theurethane conversion rate with the alcohols and the isocyanurateconversion rate (trimer conversion rate).

In this case, the urethane conversion rate is, for example, 0.1 mass %or more, preferably 0.5 mass % or more, more preferably 1 mass % ormore, and for example, 10 mass % or less, preferably 8 mass % or less,more preferably 5 mass % or less.

The isocyanurate conversion rate (trimer conversion rate) is, forexample, 5 mass % or more, preferably 7 mass % or more, more preferably10 mass % or more, and for example, 40 mass % or less, preferably 35mass % or less, more preferably 30 mass % or less.

The conversion rate of the isocyanate group of the pentamethylenediisocyanate, the urethane conversion rate, and the isocyanurateconversion rate can be obtained in conformity with Examples to bedescribed later by calculating the decreasing rate of the concentrationof the isocyanate group in the reaction liquid with respect to theconcentration of the isocyanate group of the pentamethylene diisocyanateat the time of charging in the same manner as the xylylene diisocyanate.

The modified product of the pentamethylene diisocyanate can contain amultiple molecular product containing four or more molecules of thepentamethylene diisocyanate (hereinafter, referred to as four or moremolecular product).

When the modified product of the pentamethylene diisocyanate is theisocyanurate derivative, for example, the four or more molecular productis a multiple molecular product that has a molecular weight of themolecular weight or more of a reaction product (four molecular product)of one molecule of the pentamethylene diisocyanate in addition to theisocyanurate one nuclide (to be specific, a compound in which threemolecules of the pentamethylene diisocyanate form one isocyanurate ring,that is, three molecular product of the pentamethylene diisocyanate viathe isocyanurate ring). To be specific, examples thereof include twonuclides (five molecular product), three nuclides (seven molecularproduct), and n nuclides ((2n+1) molecular product).

In the modified product of the pentamethylene diisocyanate, the contentratio of the four or more molecular product with respect to the totalamount of the modified product of the pentamethylene diisocyanate is,for example, 20 mass % or more, preferably 25 mass % or more, morepreferably 30 mass % or more, further more preferably 33 mass % or more,particularly preferably 35 mass % or more, and for example, 80 mass % orless, preferably 70 mass % or less, more preferably 65 mass % or less,further more preferably 60 mass % or less, particularly preferably 55mass % or less.

In the modified product of the pentamethylene diisocyanate, the contentratio of the four or more molecular product can be calculated bymeasuring the molecular weight distribution of the modified product ofthe pentamethylene diisocyanate based on the calibration curve of thestandard polyethylene oxide with gel permeation chromatograph (GPC)equipped with a refractive index detector (RID), and as the peak arearatio (area ratio of the four or more molecular product with respect tothe area ratio of the modified product of the pentamethylenediisocyanate) in the obtained chromatogram (chart).

In the modified product of the pentamethylene diisocyanate, the arearatio of the four or more molecular product can be obtained as the arearatio corresponding to the polyethylene oxide-based molecular weight of600 or more.

In the modified product of the pentamethylene diisocyanate, when thecontent ratio of the four or more molecular product is within theabove-described range, the polyurethane resin (described later) havingexcellent mechanical properties (hardness or the like), designproperties, and durability (chemical resistance, weather resistance, orthe like) can be obtained.

The modified product of the pentamethylene diisocyanate may containphosphorus, when the organic phosphite or the like is used as theauxiliary catalyst.

The concentration of the phosphorus of the modified product(composition) of the pentamethylene diisocyanate is, for example, 5 ppmor more, preferably 10 ppm or more, and for example, 500 ppm or less,preferably 300 ppm or less.

The concentration of the phosphorus can be obtained in conformity withExamples to be described later.

When the polyisocyanate composition consists of the modified product ofthe xylylene diisocyanate and the modified product of the pentamethylenediisocyanate (that is, in the case of the embodiment of theabove-described (1)), the polyisocyanate composition can be obtained byblending and mixing the modified product of the xylylene diisocyanateand the modified product of the pentamethylene diisocyanate by a knownmethod.

In this case, the ratio of each of the components in the polyisocyanatecomposition is adjusted as the ratio (to be specific, the ratio of thexylylene diisocyanate monomer and the pentamethylene diisocyanatemonomer) of the material monomer of each of the components.

To be more specific, the ratio of the xylylene diisocyanate with respectto the total amount (total mol) of the xylylene diisocyanate and thepentamethylene diisocyanate is, for example, 5 mol % or more, preferably10 mol % or more, more preferably 15 mol % or more, and for example, 40mol % or less, preferably 30 mol % or less, more preferably 25 mol % orless. Also, the ratio of the pentamethylene diisocyanate with respect tothe total amount (total mol) of the xylylene diisocyanate and thepentamethylene diisocyanate is, for example, 60 mol % or more,preferably 70 mol % or more, more preferably 75 mol % or more, and, forexample, 95 mol % or less, preferably 90 mol % or less, more preferably85 mol % or less.

When the ratio of the xylylene diisocyanate and the pentamethylenediisocyanate is within the above-described range, the polyurethane resin(described later) having excellent mechanical properties (hardness orthe like), design properties, and durability (chemical resistance,weather resistance, or the like) can be obtained. The structure of thecomposition of the present invention tends to have unpredictably highweather resistance and light resistance regardless of the embodimentparticularly containing the xylylene diisocyanate.

The polyisocyanate composition consisting of (2) only the modifiedproduct of the xylylene diisocyanate and the pentamethylene diisocyanateis described in detail.

The modified product of the xylylene diisocyanate and the pentamethylenediisocyanate contains the xylylene diisocyanate and the pentamethylenediisocyanate, and is a multiple molecular product containing two or moremolecules of them in total.

The modified product of the xylylene diisocyanate and the pentamethylenediisocyanate can be, for example, obtained by mixing the xylylenediisocyanate and the pentamethylene diisocyanate and modifying theobtained mixture by a method in accordance with the functional group tobe described later.

That is, the modified product of the xylylene diisocyanate and thepentamethylene diisocyanate is a co-modified product obtained bycollectively modifying the xylylene diisocyanate and the pentamethylenediisocyanate.

In the mixture of the xylylene diisocyanate and the pentamethylenediisocyanate, as the ratio of each of the components, the ratio of thexylylene diisocyanate with respect to the total amount (total mol) ofthe xylylene diisocyanate and the pentamethylene diisocyanate is, forexample, 5 mol % or more, preferably 10 mol % or more, more preferably15 mol % or more, and for example, 40 mol % or less, preferably 30 mol %or less, more preferably 25 mol % or less. Also, the ratio of thepentamethylene diisocyanate with respect to the total amount (total mol)of the xylylene diisocyanate and the pentamethylene diisocyanate is, forexample, 60 mol % or more, preferably 70 mol % or more, more preferably75 mol % or more, and, for example, 95 mol % or less, preferably 90 mol% or less, more preferably 85 mol % or less.

When the ratio of the xylylene diisocyanate and the pentamethylenediisocyanate is within the above-described range, the polyurethane resin(described later) having excellent mechanical properties (hardness orthe like), design properties, and durability (chemical resistance,weather resistance, or the like) can be obtained.

The modified product of the xylylene diisocyanate and the pentamethylenediisocyanate preferably contains at least one functional group selectedfrom the group consisting of the above-described (a) to (i) in the samemanner as the modified product of the xylylene diisocyanate describedabove: (a) isocyanurate group, (b) allophanate group, (c) biuret group,(d) urethane group, (e) urea group, (f) uretdione group, (g)iminooxadiazinedione group, (h) uretonimine group, and (i) carbodiimidegroup.

The modified product containing the functional group (isocyanurategroup) of the above-described (a) is a cotrimer of the mixture of thexylylene diisocyanate and the pentamethylene diisocyanate, and can be,for example, obtained by allowing the mixture of the xylylenediisocyanate and the pentamethylene diisocyanate to react under thepresence of a known isocyanurate-formation catalyst to be trimerized.

The modified product containing the functional group (allophanate group)of the above-described (b) is an allophanate modified product of themixture of the xylylene diisocyanate and the pentamethylenediisocyanate, and can be, for example, obtained by allowing the mixtureof the xylylene diisocyanate and the pentamethylene diisocyanate toreact with the above-described alcohols to then further react under thepresence of a known allophanate-formation catalyst.

The modified product containing the functional group (biuret group) ofthe above-described (c) is a biuret modified product of the mixture ofthe xylylene diisocyanate and the pentamethylene diisocyanate, and canbe, for example, obtained by allowing the mixture of the xylylenediisocyanate and the pentamethylene diisocyanate to react with water,tertiary alcohol (for example, t-butyl alcohol or the like), and asecondary amine (for example, dimethylamine, diethylamine, or the like).

The polyisocyanate composition containing the functional group (urethanegroup) of the above-described (d) is a polyol modified product (polyolderivative) of the mixture of the xylylene diisocyanate and thepentamethylene diisocyanate, and can be, for example, obtained byreaction of the mixture of the xylylene diisocyanate and thepentamethylene diisocyanate with a polyol component (for example, theabove-described trihydric alcohols such as trimethylolpropane).

The modified product containing the functional group (urea group) of theabove-described (e) is a polyamine modified product of the mixture ofthe xylylene diisocyanate and the pentamethylene diisocyanate, and canbe, for example, obtained by reaction of the mixture of the xylylenediisocyanate and the pentamethylene diisocyanate with water, a polyaminecomponent, or the like.

The modified product containing the functional group (uretdione group)of the above-described (f) is a uretdione modified product (dimer) ofthe mixture of the xylylene diisocyanate and the pentamethylenediisocyanate, and can be, for example, obtained by allowing the mixtureof the xylylene diisocyanate and the pentamethylene diisocyanate toreact under the presence of a known dimerization-formation catalyst tobe dimerized.

The modified product containing the functional group(iminooxadiazinedione group) of the above-described (g) is a cotrimer ofthe mixture of the xylylene diisocyanate and the pentamethylenediisocyanate, and can be, for example, obtained by allowing the mixtureof the xylylene diisocyanate and the pentamethylene diisocyanate toreact under the presence of a known iminooxadiazinedione-formationcatalyst to be trimerized.

The modified product containing the functional group (uretonimine group)of the above-described (h) is a uretonimine modified product of themixture of the xylylene diisocyanate and the pentamethylenediisocyanate, and can be, for example, obtained by reaction of themixture of the xylylene diisocyanate and the pentamethylene diisocyanatewith a carbodiimide compound.

The modified product containing the functional group (carbodiimidegroup) of the above-described (i) is a carbodiimide modified product ofthe mixture of the xylylene diisocyanate and the pentamethylenediisocyanate, and can be, for example, obtained by decarboxylationcondensation reaction of the mixture of the xylylene diisocyanate andthe pentamethylene diisocyanate.

The modified product of the xylylene diisocyanate and the pentamethylenediisocyanate may contain at least one of the functional group of theabove-described (a) to (i), and can also contain two or more functionalgroups. The modified product is produced by appropriately using theabove-described reactions in combination.

As the modified product of the xylylene diisocyanate and thepentamethylene diisocyanate, preferably, a cotrimer of the mixture ofthe xylylene diisocyanate and the pentamethylene diisocyanate is used.In other words, the modified product of the xylylene diisocyanate andthe pentamethylene diisocyanate preferably contains the cotrimer of themixture of the xylylene diisocyanate and the pentamethylenediisocyanate, more preferably consists of the cotrimer of the mixture ofthe xylylene diisocyanate and the pentamethylene diisocyanate.

When the cotrimer of the mixture of the xylylene diisocyanate and thepentamethylene diisocyanate is used, a polyurethane resin havingexcellent mechanical properties (hardness or the like) and durability(chemical resistance, weather resistance, or the like) can be obtained.

The cotrimer of the mixture of the xylylene diisocyanate and thepentamethylene diisocyanate contains a modified product containing theisocyanurate group of the above-described (a) (isocyanurate derivative)and a modified product containing the iminooxadiazinedione group of theabove-described (g) (iminooxadiazinedione derivative).

The isocyanurate derivative and the iminooxadiazinedione derivative arein the relationship of structural isomers, and the isocyanuratederivative is a symmetrical trimer and the iminooxadiazinedionederivative is an asymmetrical trimer.

An iminooxadiazinedione derivative may be produced as a by-product atthe time of the production of the isocyanurate derivative, and anisocyanurate derivative may be produced as a by-product at the time ofthe production of the iminooxadiazinedione derivative.

As the cotrimer of the mixture of the xylylene diisocyanate and thepentamethylene diisocyanate, preferably, an isocyanurate derivative ofthe xylylene diisocyanate and the pentamethylene diisocyanate is used.

The isocyanurate derivative of the xylylene diisocyanate and thepentamethylene diisocyanate is, for example, obtained by subjecting theabove-described mixture of the xylylene diisocyanate and thepentamethylene diisocyanate to isocyanurate-formation reaction under thepresence of an isocyanurate-formation catalyst.

As the isocyanurate-formation catalyst, the isocyanurate-formationcatalyst illustrated as the catalyst in the isocyanurate-formationreaction of the xylylene diisocyanate is used.

As the isocyanurate-formation catalyst, preferably, organic weak acidsalts of trialkylhydroxyalkylammonium are used, more preferably, organicweak acid salts of trimethylhydroxypropylammonium are used.

The mixing ratio (solid content) of the isocyanurate-formation catalystwith respect to 100 parts by mass of the mixture of the xylylenediisocyanate and the pentamethylene diisocyanate is, for example, 0.001parts by mass (phr) or more, preferably 0.003 parts by mass (phr) ormore, and for example, 0.05 parts by mass (phr) or less, preferably 0.03parts by mass (phr) or less.

The reaction conditions of the isocyanurate-formation reaction of themixture of the xylylene diisocyanate and the pentamethylene diisocyanateare as follows: for example, under an inert gas atmosphere such asnitrogen gas under a normal pressure (atmospheric pressure), thereaction temperature (maximum achieving temperature) is, for example,40° C. or more, preferably 60° C. or more, and for example, 90° C. orless, preferably 80° C. or less, and the reaction time is, for example,30 minutes or more, preferably 60 minutes or more, and for example, 600minutes or less, preferably 480 minutes or less.

In the above-described reaction, the above-described organic phosphiteor the like can be also blended as an auxiliary catalyst in the samemanner as the isocyanurate-formation reaction of the xylylenediisocyanate described above.

As the organic phosphite, preferably, an aromatic organic phosphite isused, more preferably, di-, tri-, or tetra-phosphites derived fromaromatic polyhydric alcohol are used, further more preferably,tetraphenyl-dipropyleneglycol-diphosphite is used.

The mixing ratio of the organic phosphite with respect to 100 parts bymass of the mixture of the xylylene diisocyanate and the pentamethylenediisocyanate is, for example, 0.001 parts by mass (phr) or more,preferably 0.005 parts by mass (phr) or more, and for example, 0.05parts by mass (phr) or less, preferably 0.03 parts by mass (phr) orless.

By blending the above-described organic phosphite as an auxiliarycatalyst, improvement of the reaction speed and the reaction rate can beachieved, and the gelation can be suppressed.

In the above-described reaction, a stabilizer such as the hinderedphenol antioxidant described above can be also added in the same manneras the isocyanurate-formation reaction of the xylylene diisocyanate.

The mixing ratio of the stabilizer with respect to 100 parts by mass ofthe mixture of the xylylene diisocyanate and the pentamethylenediisocyanate is, for example, 0.001 parts by mass (phr) or more,preferably 0.002 parts by mass (phr) or more, and for example, 0.02parts by mass (phr) or less, preferably 0.01 parts by mass (phr) orless.

In the above-described reaction, a known reaction solvent may be blendedas needed, and furthermore, a known catalyst deactivator (for example,phosphoric acid, monochloroacetic acid, dodecylbenzenesulfonic acid,paratoluenesulfonic acid, ortho-toluene sulfonic acid, benzoyl chloride,p-toluenesulfonamide, o-toluenesulfonamide, or the like) can be alsoadded at an arbitrary timing.

After the completion of the reaction, the unreacted xylylenediisocyanate and the unreacted pentamethylene diisocyanate can beremoved by a known method as needed.

To be specific, after the completion of the above-describedisocyanurate-formation reaction, the unreacted xylylene diisocyanatemonomer and the unreacted pentamethylene diisocyanate monomer can beremoved from an obtained reaction mixture of the isocyanuratederivative, the xylylene diisocyanate monomer, and the pentamethylenediisocyanate monomer by, for example, a known method such asdistillation such as thin-film distillation (Smith distillation) andextraction.

In the present invention, when the thin-film distillation is performedafter the completion of the isocyanurate-formation reaction, the yield(distillation yield) of the isocyanurate derivative obtained by thethin-film distillation is the mass of the isocyanurate derivative of thexylylene diisocyanate and the pentamethylene diisocyanate with respectto the mass of the reaction mixture, and is, for example, 5 mass % ormore, preferably 10 mass % or more, more preferably 15 mass % or more,and for example, 70 mass % or less, preferably 64 mass % or less, morepreferably 60 mass % or less.

The distillation yield of the isocyanurate derivative of the xylylenediisocyanate and the pentamethylene diisocyanate can be obtained inconformity with Examples to be described later by calculating the ratioof the mass of the isocyanurate derivative of the xylylene diisocyanateand the pentamethylene diisocyanate with respect to the mass of thereaction mixture.

In the above-described reaction, alcohols can be also blended as needed.That is, the isocyanurate derivative can be modified with the alcohols.

As the alcohols, the alcohols illustrated as the alcohols in theisocyanurate-formation reaction of the xylylene diisocyanate are used.

As the alcohols, preferably, aliphatic alcohols are used, morepreferably, monohydric and dihydric aliphatic alcohols are used, furthermore preferably, monohydric aliphatic alcohols are used.

As the aliphatic alcohols, preferably, aliphatic alcohols having 1 to 20carbon atoms are used, more preferably, aliphatic alcohols having 2 to20 carbon atoms are used, further more preferably, aliphatic alcoholshaving 2 to 8 carbon atoms are used.

As the aliphatic alcohols, preferably, branched monohydric and dihydricaliphatic alcohols are used, more preferably, branched monohydricaliphatic alcohols are used, particularly preferably, isobutanol (alsoknown as: isobutyl alcohol, IBA) is used.

The alcohols are blended so that the average functionality is two ormore in the isocyanurate derivative of the xylylene diisocyanate and thepentamethylene diisocyanate, and the mixing ratio thereof with respectto 100 parts by mass of the mixture of the xylylene diisocyanate and thepentamethylene diisocyanate is, for example, 0.1 parts by mass or more,preferably 1.0 part by mass or more, more preferably 1.5 parts by massor more, and for example, 10 parts by mass or less, preferably 8.0 partsby mass or less.

In the reaction, the mixture of the xylylene diisocyanate and thepentamethylene diisocyanate, and the alcohols are blended so that theequivalent ratio (NCO/OH) of the isocyanate group (total amount) of thexylylene diisocyanate and the pentamethylene diisocyanate with respectto the hydroxy group of the alcohols is, for example, 5 or more,preferably 10 or more, more preferably 20 or more, and usually 1000 orless, preferably 600 or less, more preferably 100 or less.

Examples of the method for modifying the isocyanurate derivative of thexylylene diisocyanate and the pentamethylene diisocyanate with thealcohols include a method in which first, the mixture of the xylylenediisocyanate and the pentamethylene diisocyanate is allowed to reactwith the alcohols; next, the isocyanurate-formation reaction isperformed under the presence of the isocyanurate-formation catalyst; andthereafter, the unreacted xylylene diisocyanate and the unreactedpentamethylene diisocyanate are removed in the same manner as theisocyanurate-formation reaction of the xylylene diisocyanate describedabove, a method in which first, only one of the xylylene diisocyanate orthe pentamethylene diisocyanate is allowed to react with the alcohols;next the other isocyanate is blended therein; then, theisocyanurate-formation reaction is performed under the presence of theisocyanurate-formation catalyst; and thereafter, the unreacted xylylenediisocyanate and the unreacted pentamethylene diisocyanate are removed,and a method in which first, only the mixture of the xylylenediisocyanate and the pentamethylene diisocyanate is subjected toisocyanurate-formation reaction by the above-described method; then, theunreacted xylylene diisocyanate and the unreacted pentamethylenediisocyanate are removed; and thereafter, the obtained polyisocyanurateis allowed to react with the alcohols.

Preferably, first, the mixture of the xylylene diisocyanate and thepentamethylene diisocyanate is allowed to react with the alcohols; next,the isocyanurate-formation reaction is performed under the presence ofthe isocyanurate-formation catalyst; and thereafter, the unreactedxylylene diisocyanate and the unreacted pentamethylene diisocyanate areremoved.

The reaction of the mixture of the xylylene diisocyanate and thepentamethylene diisocyanate with the alcohols is the urethane-formationreaction (including allophanate-formation reaction), and the reactionconditions are as follows: for example, under an inert gas atmospheresuch as nitrogen gas under a normal pressure (atmospheric pressure), thereaction temperature is, for example, room temperature (for example, 25°C.) or more, preferably 40° C. or more, and for example, 100° C. orless, preferably 90° C. or less, and the reaction time is, for example,0.05 hours or more, preferably 0.2 hours or more, and for example, 10hours or less, preferably 6 hours or less, more preferably 3 hours orless.

In the above-described urethane-formation reaction, for example, theabove-described urethane-formation catalyst such as amines and anorganic metal compound may be added as needed.

In the method, the isocyanurate-formation catalyst is blended into thereaction liquid to be obtained at the above-described mixing ratio, andthe reaction product of the mixture of the xylylene diisocyanate and thepentamethylene diisocyanate, and the alcohols is subjected toisocyanurate-formation reaction. The reaction conditions in theisocyanurate-formation reaction are the same as those described above.After the completion of the reaction, the unreacted xylylenediisocyanate and the unreacted pentamethylene diisocyanate are removedby a known removing method such as distillation as needed.

In this manner, the isocyanurate derivative of the xylylene diisocyanateand the pentamethylene diisocyanate that is modified with the alcoholscan be obtained.

For example, when the method in which only the mixture of the xylylenediisocyanate and the pentamethylene diisocyanate is subjected toisocyanurate-formation reaction; then, the unreacted xylylenediisocyanate and the unreacted pentamethylene diisocyanate are removed;and thereafter, the obtained polyisocyanate is allowed to react with thealcohols (the latter method in the description above) is used, theisocyanurate derivative of the xylylene diisocyanate and thepentamethylene diisocyanate reacts with the alcohols. The reaction isthe urethane-formation reaction, and the reaction is performed under thereaction conditions of the urethane-formation reaction described above.

In this manner, the isocyanurate derivative of the xylylene diisocyanateand the pentamethylene diisocyanate that is modified with the alcoholscan be also produced.

When the isocyanurate derivative of the xylylene diisocyanate and thepentamethylene diisocyanate is modified with the alcohols, anallophanate derivative of the xylylene diisocyanate and thepentamethylene diisocyanate may be obtained as a by-product. In thiscase, the isocyanurate derivative of the xylylene diisocyanate and thepentamethylene diisocyanate contains the allophanate derivativeconsisting of the xylylene diisocyanate and the pentamethylenediisocyanate as an auxiliary component inevitably contained. In otherwords, when the isocyanurate derivative of the xylylene diisocyanate andthe pentamethylene diisocyanate is modified with the alcohols, anisocyanurate composition containing the isocyanurate derivative of thexylylene diisocyanate and the pentamethylene diisocyanate, and theallophanate derivative of the xylylene diisocyanate and thepentamethylene diisocyanate is obtained.

In the isocyanurate derivative of the xylylene diisocyanate and thepentamethylene diisocyanate that is modified with the alcohols, themodification amount (alcohol modification rate of the isocyanuratederivative) of the alcohols with respect to the isocyanurate derivativeis, for example, 0.5 mass % or more, preferably 1.0 mass % or more, morepreferably 3.0 mass % or more, further more preferably 4.0 mass % ormore, and for example, 15 mass % or less, preferably 10 mass % or less,more preferably 6.0 mass % or less.

The modification amount (alcohol modification rate) of the alcohols withrespect to the isocyanurate derivative can be obtained by the samecalculation formula as that of the alcohol modification rate in theisocyanurate derivative of the xylylene diisocyanate described above.

In the same manner as the description above, the alcohol modificationrate can be also calculated by ¹H-NMR measurement.

As the isocyanurate derivative of the xylylene diisocyanate and thepentamethylene diisocyanate, any one of the isocyanurate derivative ofthe xylylene diisocyanate and the pentamethylene diisocyanate that isnot essentially modified with the alcohols and the isocyanuratederivative of the xylylene diisocyanate and the pentamethylenediisocyanate that is modified with the alcohols may be used. In view ofcuring properties, adhesive properties, and chemical resistance,preferably, the isocyanurate derivative of the xylylene diisocyanate andthe pentamethylene diisocyanate that is not essentially modified withthe alcohols is used, and in view of weather resistance, preferably, theisocyanurate derivative of the xylylene diisocyanate and thepentamethylene diisocyanate that is modified with the alcohols is used.

As the ratio of the xylylene diisocyanate and the pentamethylenediisocyanate that are contained in the isocyanurate derivative of thexylylene diisocyanate and the pentamethylene diisocyanate, the ratio ofthe xylylene diisocyanate with respect to the total amount (total mol)of the xylylene diisocyanate and the pentamethylene diisocyanate is 5mol % or more, preferably 10 mol % or more, more preferably 15 mol % ormore, and for example, 40 mol % or less, preferably 30 mol % or less,more preferably 25 mol % or less. The ratio of the pentamethylenediisocyanate with respect to the total amount (total mol) of thexylylene diisocyanate and the pentamethylene diisocyanate is, forexample, 60 mol % or more, preferably 70 mol % or more, more preferably75 mol % or more, and for example, 95 mol % or less, preferably 90 mol %or less, more preferably 85 mol % or less.

When the ratio of the xylylene diisocyanate and the pentamethylenediisocyanate is within the above-described range, the polyurethane resin(described later) having excellent mechanical properties (hardness orthe like), design properties, and durability (chemical resistance,weather resistance, or the like) can be obtained. The structure of thecomposition of the present invention tends to have unpredictably highweather resistance and light resistance regardless of the embodimentparticularly containing the xylylene diisocyanate.

The ratio of the xylylene diisocyanate and the pentamethylenediisocyanate contained in the isocyanurate derivative of the xylylenediisocyanate and the pentamethylene diisocyanate can be obtained byproducing the isocyanurate derivative as described above and then,measuring the amount of the unreacted monomer by GCMS analysis (massanalysis) to be subtracted from the charged amount in conformity withExamples to be described later.

The concentration of the isocyanate group (solid content of 100 mass %)of the isocyanurate reaction liquid (before distillation) in theisocyanurate derivative of the xylylene diisocyanate and thepentamethylene diisocyanate is, for example, 20 mass % or more,preferably 25 mass % or more, more preferably 30 mass % or more, and forexample, 50 mass % or less, preferably 45 mass % or less.

The concentration of the isocyanate group (solid content of 100 mass %)in the isocyanurate derivative of the xylylene diisocyanate and thepentamethylene diisocyanate can be obtained in conformity with Examplesto be described later.

In the isocyanurate derivative of the xylylene diisocyanate and thepentamethylene diisocyanate, the concentration of the isocyanate monomer(concentration of the unreacted xylylene diisocyanate and the unreactedpentamethylene diisocyanate) is, for example, 2 mass % or less,preferably 1 mass % or less, more preferably 0.5 mass % or less.

In the isocyanurate derivative of the xylylene diisocyanate and thepentamethylene diisocyanate, the conversion rate (reaction rate) of theisocyanate group is, for example, 5 mass % or more, preferably 10 mass %or more, and for example, 40 mass % or less, preferably 30 mass % orless.

When the isocyanurate derivative of the xylylene diisocyanate and thepentamethylene diisocyanate is not essentially modified with thealcohols, the conversion rate (reaction rate) of the isocyanate group issubstantially the same as the isocyanurate conversion rate (trimerconversion rate).

That is, the isocyanurate conversion rate (trimer conversion rate) is,for example, 5 mass % or more, preferably 10 mass % or more, and forexample, 4) mass % or less, preferably 30 mass % or less.

Meanwhile, when the isocyanurate derivative of the xylylene diisocyanateand the pentamethylene diisocyanate is modified with the alcohols, theconversion rate (reaction rate) of the isocyanate group is the totalvalue of the urethane conversion rate with the alcohols and theisocyanurate conversion rate (trimer conversion rate).

In this case, the urethane conversion rate is, for example, 1 mass % ormore, preferably 2 mass % or more, more preferably 3 mass % or more, andfor example, 10 mass % or less, preferably 8 mass % or less, morepreferably 5 mass % or less.

The isocyanurate conversion rate (trimer conversion rate) is, forexample, 5 mass % or more, preferably 10 mass % or more, and forexample, 40 mass % or less, preferably 30 mass % or less.

The conversion rate of the isocyanate group, the urethane conversionrate, and the isocyanurate conversion rate can be obtained in conformitywith Examples to be described later by calculating the decreasing rateof the concentration of the isocyanate group in the reaction liquid withrespect to the concentration of the isocyanate group of the xylylenediisocyanate and the pentamethylene diisocyanate at the time of chargingin the same manner as the xylylene diisocyanate.

The modified product of the xylylene diisocyanate and the pentamethylenediisocyanate can contain a multiple molecular product containing four ormore molecules of the xylylene diisocyanate and/or the pentamethylenediisocyanate (hereinafter, referred to as four or more molecularproduct).

When the modified product of the xylylene diisocyanate and thepentamethylene diisocyanate is the isocyanurate derivative, for example,the four or more molecular product is a multiple molecular product thathas a molecular weight of the molecular weight or more of a reactionproduct (four molecular product) of one molecule of the xylylenediisocyanate or the pentamethylene diisocyanate in addition to theisocyanurate one nuclide (to be specific, a compound in which threemolecules in total of the xylylene diisocyanate and the pentamethylenediisocyanate form one isocyanurate ring, that is, three molecularproduct of the xylylene diisocyanate and the pentamethylene diisocyanatevia the isocyanurate ring). To be specific, examples thereof include twonuclides (five molecular product), three nuclides (seven molecularproduct), and n nuclides ((2n+1) molecular product).

In the modified product of the xylylene diisocyanate and thepentamethylene diisocyanate, the content ratio of the four or moremolecular product with respect to the total amount of the modifiedproduct of the xylylene diisocyanate and the pentamethylene diisocyanateis, for example, 20 mass % or more, preferably 25 mass % or more, morepreferably 30 mass % or more, further more preferably 33 mass % or more,particularly preferably 35 mass % or more, and for example, 80 mass % orless, preferably 70 mass % or less, more preferably 65 mass % or less,further more preferably 60 mass % or less, particularly preferably 55mass % or less.

In the modified product of the xylylene diisocyanate and thepentamethylene diisocyanate, the content ratio of the four or moremolecular product can be calculated by measuring the molecular weightdistribution of the modified product of the xylylene diisocyanate andthe pentamethylene diisocyanate based on the calibration curve of thestandard polyethylene oxide with gel permeation chromatograph (GPC)equipped with a refractive index detector (RID), and as the peak arearatio (area ratio of the four or more molecular product with respect tothe area ratio of the modified product of the xylylene diisocyanate andthe pentamethylene diisocyanate) in the obtained chromatogram (chart).

In the modified product of the xylylene diisocyanate and thepentamethylene diisocyanate, the area ratio of the four or moremolecular product can be obtained as the area ratio corresponding to thepolyethylene oxide-based molecular weight of 600 or more.

In the modified product of the xylylene diisocyanate and thepentamethylene diisocyanate, when the content ratio of the four or moremolecular product is within the above-described range, the polyurethaneresin (described later) having excellent mechanical properties (hardnessor the like), design properties, and durability (chemical resistance,weather resistance, or the like) can be obtained.

The modified product of the xylylene diisocyanate and the pentamethylenediisocyanate may contain phosphorus, when the organic phosphite or thelike is used as the auxiliary catalyst.

The concentration of the phosphorus of the modified product(composition) of the xylylene diisocyanate and the pentamethylenediisocyanate is, for example, 5 ppm or more, preferably 10 ppm or more,and for example, 500 ppm or less, preferably 300 ppm or less.

The concentration of the phosphorus can be obtained in conformity withExamples to be described later.

In the polyisocyanate composition, the ratio of the xylylenediisocyanate and the pentamethylene diisocyanate is within theabove-described range, so that the polyurethane resin (described later)having excellent mechanical properties (hardness or the like), designproperties, and durability (chemical resistance, weather resistance, orthe like) can be obtained.

In the description above, the method in which the xylylene diisocyanateand the pentamethylene diisocyanate are mixed, and the obtained mixtureis modified is described. Alternatively, for example, without beingmixed in advance, the xylylene diisocyanate, the pentamethylenediisocyanate, and various catalysts are collectively blended to react,so that the modified product of the xylylene diisocyanate and thepentamethylene diisocyanate can be also obtained.

The polyisocyanate composition consisting of (3) the modified product ofthe xylylene diisocyanate and/or the modified product of thepentamethylene diisocyanate, and the modified product of the xylylenediisocyanate and the pentamethylene diisocyanate is described in detail.

The polyisocyanate composition can contain the modified product of thexylylene diisocyanate described above and/or the modified product of thepentamethylene diisocyanate described above, and the modified product ofthe xylylene diisocyanate and the pentamethylene diisocyanate describedabove.

The polyisocyanate composition can be, for example, obtained by blendingand mixing the modified product of the xylylene diisocyanate describedabove and/or the modified product of the pentamethylene diisocyanatedescribed above and the modified product of the xylylene diisocyanateand the pentamethylene diisocyanate described above by a known method.

In this case, the mixing ratio of each of the components is adjusted asthe ratio (to be specific, the ratio of the xylylene diisocyanatemonomer and the pentamethylene diisocyanate mononer) of the materialmonomer of each of the components.

To be more specific, the ratio of the xylylene diisocyanate with respectto the total amount (total mol) of the xylylene diisocyanate and thepentamethylene diisocyanate is, for example, 5 mol % or more, preferably10 mol % or more, more preferably 15 mol % or more, and for example, 40mol % or less, preferably 30 mol % or less, more preferably 25 mol % orless. Also, the ratio of the pentamethylene diisocyanate with respect tothe total amount (total mol) of the xylylene diisocyanate and thepentamethylene diisocyanate is, for example, 60 mol % or more,preferably 70 mol % or more, more preferably 75 mol % or more, and, forexample, 95 mol % or less, preferably 90 mol % or less, more preferably85 mol % or less.

When the ratio of the xylylene diisocyanate and the pentamethylenediisocyanate is within the above-described range, the polyurethane resin(described later) having excellent mechanical properties (hardness orthe like), design properties, and durability (chemical resistance,weather resistance, or the like) can be obtained. The structure of thecomposition of the present invention tends to have unpredictably highweather resistance and light resistance regardless of the embodimentparticularly containing the xylylene diisocyanate.

The polyisocyanate composition (polyisocyanate composition consisting ofthe modified product of the xylylene diisocyanate, the modified productof the pentamethylene diisocyanate, and the modified product of thexylylene diisocyanate and the pentamethylene diisocyanate) of theembodiment of the above-described (3) can be also produced by, forexample, excessively blending the xylylene diisocyanate or thepentamethylene diisocyanate in the production of the modified product ofthe xylylene diisocyanate and the pentamethylene diisocyanate describedabove.

That is, at the time of the production of the modified product of thexylylene diisocyanate and the pentamethylene diisocyanate describedabove, when the xylylene diisocyanate or the pentamethylene diisocyanateis excessively blended, first, the xylylene diisocyanate and thepentamethylene diisocyanate are collectively modified, so that themodified product of the xylylene diisocyanate and the pentamethylenediisocyanate is obtained. Thereafter, excessive (that is, free) xylylenediisocyanate or pentamethylene diisocyanate is modified, so that themodified product of the xylylene diisocyanate or the modified product ofthe pentamethylene diisocyanate is obtained.

In this case, the mixing ratio of the xylylene diisocyanate and thepentamethylene diisocyanate is adjusted within the above-describedrange.

In the polyisocyanate composition, the content ratio of the modifiedproduct of the xylylene diisocyanate and the pentamethylene diisocyanateis, for example, 1 mass % or more, preferably 5 mass % or more, morepreferably 10 mass % or more, and for example, 99 mass % or less,preferably 95 mass % or less, more preferably 90 mass % or less.

When the content ratio of the modified product of the xylylenediisocyanate and the pentamethylene diisocyanate is within theabove-described range, the polyurethane resin (described later) havingmore excellent mechanical properties (hardness or the like), designproperties, and durability (chemical resistance, weather resistance, orthe like) can be obtained.

As the polyisocyanate composition, any one of the polyisocyanatecompositions of the above-described (1) to (3) may be used. Preferably,the polyisocyanate composition of the embodiment of the above-described(1) is used.

That is, the polyisocyanate composition preferably consists of themodified product of the xylylene diisocyanate and the modified productof the pentamethylene diisocyanate.

When the polyisocyanate composition of the above-described (1) is used,the polyurethane resin (described later) having more excellentmechanical properties (hardness or the like), design properties, anddurability (chemical resistance, weather resistance, or the like) can beobtained.

In the polyisocyanate composition, as the ratio of the xylylenediisocyanate and the pentamethylene diisocyanate, the ratio of thexylylene diisocyanate with respect to the total amount (total mol) ofthe xylylene diisocyanate and the pentamethylene diisocyanate is, forexample, 5 mol % or more, preferably 10 mol % or more, more preferably15 mol % or more, and for example, 40 mol % or less, preferably 30 mol %or less, more preferably 25 mol % or less. Also, the ratio of thepentamethylene diisocyanate with respect to the total amount (total mol)of the xylylene diisocyanate and the pentamethylene diisocyanate is, forexample, 60 mol % or more, preferably 70 mol % or more, more preferably75 mol % or more, and, for example, 95 mol % or less, preferably 90 mol% or less, more preferably 85 mol % or less.

When the ratio of the xylylene diisocyanate and the pentamethylenediisocyanate is within the above-described range, the polyurethane resin(described later) having excellent mechanical properties (hardness orthe like), design properties, and durability (chemical resistance,weather resistance, or the like) can be obtained.

The polyisocyanate composition can contain a multiple molecular productcontaining four or more molecules of the xylylene diisocyanate and/orthe pentamethylene diisocyanate (hereinafter, referred to as four ormore molecular product).

In the polyisocyanate composition, the content ratio of the four or moremolecular product with respect to the total amount of the polyisocyanatecomposition is, for example, 20 mass % or more, preferably 25 mass % ormore, more preferably 30 mass % or more, further more preferably 33 mass% or more, particularly preferably 35 mass % or more, and for example,80 mass % or less, preferably 70 mass % or less, more preferably 65 mass% or less, further more preferably 60 mass % or less, particularlypreferably 55 mass % or less.

In the polyisocyanate composition, the content ratio of the four or moremolecular product can be calculated by measuring the molecular weightdistribution of the polyisocyanate composition based on the calibrationcurve of the standard polyethylene oxide with gel permeationchromatograph (GPC) mounted with a refractive index detector (RID), andas the peak area ratio (area ratio of the four or more molecular productwith respect to the area ratio of the polyisocyanate composition) in theobtained chromatogram (chart).

In the polyisocyanate composition, the area ratio of the four or moremolecular product can be obtained as the area ratio corresponding to thepolyethylene oxide-based molecular weight of 600 or more.

The content ratio of the four or more molecular product of thepolyisocyanate composition can be obtained by directly subjecting thepolyisocyanate composition to gel permeation chromatograph measurement.

Also, for example, when the polyisocyanate composition contains themodified product of the xylylene diisocyanate and the modified productof the pentamethylene diisocyanate (for example, in the case of thepolyisocyanate composition of the above-described (1)), each of themodified product of the xylylene diisocyanate and the modified productof the pentamethylene diisocyanate may be measured with gel permeationchromatograph, and the content ratio of the four or more molecularproduct of the polyisocyanate composition may be calculated from thecontent ratio of the four or more molecular product to be obtained andthe mixing ratio.

To be specific, the ratio (mole ratio) of the xylylene diisocyanate ismultiplied by the content ratio of the four or more molecular product ofthe modified product of the xylylene diisocyanate, and meanwhile, theratio (mole ratio) of the pentamethylene diisocyanate is multiplied bythe content ratio of the four or more molecular product of the modifiedproduct of the pentamethylene diisocyanate. The resulting values can beadded up to make the content ratio of the four or more molecular productof the polyisocyanate composition.

In the polyisocyanate composition, when the content ratio of the four ormore molecular product is within the above-described range, thepolyurethane resin (described later) having excellent mechanicalproperties (hardness or the like), design properties, and durability(chemical resistance, weather resistance, or the like) can be obtained.

In the polyisocyanate composition, the multiple molecular product offour or more molecules preferably contains the multiple molecularproduct of the xylylene diisocyanate of four or more molecules (that is,multiple molecular product that does not contain the pentamethylenediisocyanate and contains the xylylene diisocyanate of four or moremolecules).

The content ratio of the multiple molecular product of the xylylenediisocyanate of four or more molecules (hereinafter, referred to as fouror more molecular product of the xylylene diisocyanate) with respect tothe total amount of the four or more molecular product is, for example,1 mass % or more, preferably 5 mass % or more, more preferably 10 mass %or more, further more preferably 15 mass % or more, and for example, 50mass % or less, preferably 45 mass % or less, more preferably 43 mass %or less, further more preferably 40 mass % or less, further morepreferably 30 mass % or less, particularly preferably 25 mass % or less.

When the content ratio of the four or more molecular product of thexylylene diisocyanate is within the above-described range, thepolyurethane resin (described later) having excellent mechanicalproperties (hardness or the like), design properties, and durability(chemical resistance, weather resistance, or the like) can be obtained.

The content ratio of the four or more molecular product of the xylylenediisocyanate can be obtained by directly subjecting the polyisocyanatecomposition to gel permeation chromatograph measurement in conformitywith Examples to be described later.

Furthermore, a known additive can be also blended to the polyisocyanatecomposition at an appropriate ratio as needed. Examples thereof includestorage stabilizers (o-toluenesulfonamide, p-toluenesulfonamide, or thelike), plasticizers, blocking inhibitors, heat-resistant stabilizers,light-resistant stabilizers, antioxidants, release agents, catalysts,pigments, dyes, lubricants, fillers, and hydrolysis inhibitors.

The additive can be, for example, blended in at least any one of themodified product of the xylylene diisocyanate, the modified product ofthe pentamethylene diisocyanate, and the modified product of thexylylene diisocyanate and the pentamethylene diisocyanate, or a mixturethereof.

The polyisocyanate composition does not contain a solvent, and can bediluted with an organic solvent as needed.

Examples of the organic solvent include ketones such as acetone, methylethyl ketone, methyl isobutyl ketone, and cyclohexanone; nitriles suchas acetonitrile; alkyl esters such as methyl acetate, ethyl acetate,butyl acetate, and isobutyl acetate; aliphatic hydrocarbons such asn-hexane, n-heptane, and octane; alicyclic hydrocarbons such ascyclohexane and methyl cyclohexane; aromatic hydrocarbons such astoluene, xylene, and ethyl benzene; glycol ether esters such as methylcellosolve acetate, ethyl cellosolve acetate, methyl carbitol acetate,ethyl carbitol acetate, ethylene glycol ethyl ether acetate, propyleneglycol methyl ether acetate, 3-methyl-3-methoxybutylacetate, andethyl-3-ethoxypropionate; ethers such as diethyl ether, tetrahydrofuran,and dioxane; halogenated aliphatic hydrocarbons such as methyl chloride,methylene chloride, chloroform, carbon tetrachloride, methyl bromide,methylene iodide, and dichloroethane; and aprotic polar solvents such asN-methyl pyrrolidone, dimethyl formamide, N,N′-dimethylacetamide,dimethyl sulfoxide, and hexamethylphosphonylamide.

Furthermore, examples of the organic solvent include non-polar solvents(non-polar organic solvents). Examples of the non-polar solvents includenon-polar organic solvents having an aniline point of, for example, 10to 70° C., preferably 12 to 65° C. with low toxic and weak solubility,including aliphatic and naphthene-type hydrocarbonic organic solventsand vegetable oils represented by terpene oil.

The non-polar organic solvent can be available as a commerciallyavailable product. Examples of the commercially available productthereof include petroleum hydrocarbonate organic solvents such as HAWS(manufactured by Shell Chemicals Japan, aniline point of 15° C.),SWAZOLE 310 (manufactured by Maruzen Petrochemical Co., Ltd., anilinepoint of 16° C.), ESSO NAPHTHA No. 6 (manufactured by Exxon Chemical,Co., Ltd., aniline point of 43° C.), LAWS (manufactured by ShellChemicals Japan, aniline point of 43° C.), ESSO NAPHTHA No. 5(manufactured by Exxon Chemical, Co., Ltd., aniline point of 55° C.),and PEGASOL 3040 (manufactured by Mobil Oil Corporation, aniline pointof 55° C.); and in addition, terpene oils such as methyl cyclohexane(aniline point of 40° C.), ethylcyclohexane (aniline point of 44° C.),and GUM TURPENTINE N (manufactured by YASUHARA CHEMICAL CO., LTD.,aniline point of 27° C.).

The polyisocyanate composition can be mixed with these organic solventsat an arbitrary ratio.

When the polyisocyanate composition is diluted with the organic solvent,for example, the organic solvent may be blended into both or any one ofthe derivative of the xylylene diisocyanate and the derivative of thealiphatic polyisocyanate in advance; may be blended at the time ofblending of the derivative of the xylylene diisocyanate and thederivative of the aliphatic polyisocyanate; and furthermore, may beseparately blended into the polyisocyanate composition that is obtainedafter blending the derivative of the xylylene diisocyanate and thederivative of the aliphatic polyisocyanate.

When the polyisocyanate composition is diluted with the organic solvent,the concentration of the polyisocyanate composition is, for example, 20mass % or more, preferably 30 mass % or more, and for example, 95 mass %or less, preferably 90 mass % or less.

In this case, the viscosity at 25° C. thereof is adjusted to, forexample, 10 mPa·s or more, preferably 20 mPa·s or more, and for example,10000 mPa·s or less, preferably 5000 mPa·s or less.

According to the polyisocyanate composition, the polyurethane resinhaving excellent mechanical properties (hardness or the like), designproperties, and durability (chemical resistance, weather resistance, orthe like) can be obtained.

Thus, the polyisocyanate composition is preferably used in theproduction of the polyurethane resin.

The polyurethane resin can be obtained by allowing the above-describedpolyisocyanate composition to react with an active hydrogengroup-containing compound.

In the present invention, the active hydrogen group-containing compoundis, for example, an organic compound having one or more of activehydrogen group(s) such as hydrogen group, mercapto group, and aminogroup in a molecule.

Examples of the active hydrogen group-containing compound include monoolcomponents, polyol components, monothiol components, polythiolcomponents, monoamine components, and polyamine components. Preferably,monool components and polyol components are used, more preferably,polyol components are used.

In the present invention, an example of the monool component includes acompound having one hydroxyl group and having a number average molecularweight of below 400, preferably below 300. To be specific, examplesthereof include aliphatic monoalcohols such as methanol, ethanol,propanol, n-butanol, and isobutanol and hydroxyl group-containingunsaturated compounds such as hydroxyethyl (meth)acrylate, hydroxypropyl(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritoltri(meth)acrylate, and dipentaerythritol penta(meth) acrylate.

In the present invention, examples of the polyol component include lowmolecular weight polyols and high molecular weight polyols.

The low molecular weight polyol is a compound having two or morehydroxyl groups and having a number average molecular weight of below300, preferably below 400. Examples thereof include dihydric alcoholssuch as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butyleneglycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol,1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol,2,2,2-trimethylpentanediol, 3,3-dimethylolheptane, alkane (C7 to 20)diol, 1,3- or 1,4-cyclohexanedimethanol and a mixture thereof, 1,3- or1,4-cyclohexanediol and a mixture thereof, hydrogenated bisphenol A,1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A,diethylene glycol, triethylene glycol, and dipropylene glycol; trihydricalcohols such as glycerin, trimethylolpropane, and triisopropanolamine;tetrahydric alcohols such as tetramethylolmethane (pentaerythritol), anddiglycerin; pentahydric alcohols such as xylitol; hexahydric alcoholssuch as sorbitol, mannitol, allitol, iditol, dulcitol, altritol,inositol, and dipentaerythritol; heptahydric alcohols such as perseitol;and octahydric alcohols such as sucrose.

These low molecular weight polyols can be used alone or in combinationof two or more.

The high molecular weight polyol is a compound having two or morehydroxyl groups and having a number average molecular weight of 300 ormore, preferably 400 or more, further more preferably 500 or more.Examples thereof include polyether polyol (for example, polyoxyalkylenepolyol, polytetramethylene ether polyol, or the like), polyester polyol(for example, polyester adipate polyol, polyester phthalate polyol,lactone polyester polyol, or the like), polycarbonate polyol,polyurethane polyol (for example, polyol obtained by urethane-modifyingpolyether polyol, polyester polyol, and polycarbonate polyol withpolyisocyanate), epoxy polyol, vegetable oil polyol, polyolefin polyol,acrylic polyol, and vinyl monomer-modified polyol.

These high molecular weight polyols can be used alone or in combinationof two or more.

As the high molecular weight polyol, preferably, acrylic polyol is used.

The polyurethane resin can be, for example, produced by a polymerizationmethod such as bulk polymerization and solution polymerization.

In the bulk polymerization, for example, the polyisocyanate compositionis stirred under a nitrogen gas stream, and the active hydrogengroup-containing compound is added thereto to react at a reactiontemperature of 50 to 250° C., further more preferably 50 to 200° C. for0.5 to 15 hours.

In the solution polymerization, the polyisocyanate composition and theactive hydrogen group-containing compound are added to the organicsolvent illustrated as the organic solvent used in the dilution of thepolyisocyanate composition to react at a reaction temperature of 50 to120° C., preferably 50 to 100° C. for 0.5 to 15 hours.

Furthermore, in the above-described polymerization reaction, forexample, the above-described urethane-formation catalyst may be added asneeded.

In the bulk polymerization and the solution polymerization, for example,the polyisocyanate composition and the active hydrogen group-containingcompound are blended so that the equivalent ratio (NCO/active hydrogengroup) of the isocyanate group in the polyisocyanate composition withrespect to the active hydrogen group (hydroxyl group, mercapto group,and amino group) in the active hydrogen group-containing compound is,for example, 0.75 to 1.3, preferably 0.9 to 1.1.

When the above-described polymerization reaction is performed moreindustrially, the polyurethane resin can be obtained by a known methodsuch as one shot method and prepolymer method.

In the one shot method, for example, the polyisocyanate composition andthe active hydrogen group-containing compound are formulated (mixed) sothat the equivalent ratio (NCO/active hydrogen group) of the isocyanategroup in the polyisocyanate composition with respect to the activehydrogen group (hydroxyl group, mercapto group, and amino group) in theactive hydrogen group-containing compound is, for example, 0.75 to 1.3,preferably 0.9 to 1.1 to be then subjected to curing reaction at, forexample, room temperature to 250° C., preferably room temperature to200° C. for, for example, 5 minutes to 72 hours, preferably 4 to 24hours. The curing temperature may be fixed, or can be graduallyincreased or cooled.

In the prepolymer method, for example, first, the polyisocyanatecomposition reacts with a part (preferably, high molecular weightpolyol) of the active hydrogen group-containing compound, therebysynthesizing an isocyanate group-terminated prepolymer having anisocyanate group at the end of the molecule. Next, the obtainedisocyanate group-terminated prepolymer reacts with a remaining portion(preferably, low molecular weight polyol and/or polyamine component) ofthe active hydrogen group-containing compound to be subjected to a chainextension reaction. In the prepolymer method, the remaining portion ofthe active hydrogen group-containing compound can be used as a chainextension agent.

To synthesize the isocyanate group-terminated prepolymer, thepolyisocyanate composition and a part of the active hydrogengroup-containing compound are formulated (mixed) so that the equivalentratio (NCO/active hydrogen group) of the isocyanate group in thepolyisocyanate composition with respect to the active hydrogen group ina part of the active hydrogen group-containing compound is, for example,1.1 to 20, preferably 1.3 to 10, further more preferably 1.3 to 6 tothen react in a reaction vessel at, for example, room temperature to150° C., preferably 50 to 120° C., for, for example, 0.5 to 18 hours,preferably 2 to 10 hours. In the reaction, the above-describedurethane-formation catalyst may be added as needed, and after thecompletion of the reaction, the unreacted polyisocyanate composition canbe removed by, for example, a known removing method such as distillationand extraction as needed.

Next, to react the obtained isocyanate group-terminated prepolymer withthe remaining portion of the active hydrogen group-containing compound,the isocyanate group-terminated prepolymer and the remaining portion ofthe active hydrogen group-containing compound are formulated (mixed) sothat the equivalent ratio (NCO/active hydrogen group) of the isocyanategroup in the isocyanate group-terminated prepolymer with respect to theactive hydrogen group in the remaining portion of the active hydrogengroup-containing compound is, for example, 0.75 to 1.3, preferably 0.9to 1.1 to be then subjected to curing reaction at, for example, roomtemperature to 250° C., preferably room temperature to 200° C. for, forexample, 5 minutes to 72 hours, preferably 1 to 24 hours.

In this manner, the polyurethane resin can be obtained.

When the polyurethane resin is produced, furthermore, a known additivecan be added at an appropriate ratio as needed. Examples thereof includeplasticizers, blocking inhibitors, heat-resistant stabilizers,light-resistant stabilizers, antioxidants, release agents, catalysts,moreover, pigments, dyes, lubricants, fillers, and hydrolysisinhibitors. These additives may be added at the time of synthesis ofeach of the components, at the time of mixing and dissolution of each ofthe components, and furthermore, after the synthesis.

The polyurethane resin is produced by using the polyisocyanatecomposition of the present invention, so that it has excellentmechanical properties (hardness or the like), design properties, anddurability (chemical resistance, weather resistance, or the like).

Thus, the polyisocyanate composition and the polyurethane resindescribed above can be used in various industrial fields.

To be specific, the polyurethane resin and the polyisocyanatecomposition described above can be preferably used as two-componentcurable polyurethane and a curing agent thereof such as coatings,adhesives for industrial purposes, adhesives for packing, hot meltadhesives, pressure-sensitive adhesives, overprint varnish (OP varnish),ink, sealant, and binder resins.

To be more specific, when the polyurethane resin and the polyisocyanatecomposition described above are used as the coatings, examples thereofinclude coatings for plastic, coatings for car exterior, coatings forcar interior, coatings for electric and electronic material, coatingsfor optical material (lens or the like), coatings for building material,glass coatings, wood coatings, film coatings, ink coatings, artificialleather coatings (coating agent), and can coatings (coating agent).

Examples of the above-described coatings for plastic include coatingsfor casing (cell phone, smart phone, personal computer, tablet, or thelike), coatings for car component (car interior material, headlamp, orthe like), coatings for household electric appliance, coatings for robotmaterial, coatings for furniture, coatings for stationery, coatings foreyewear material (lens or the like), coatings for sport member (golfball or the like), coatings for band (watch band or the like), andcoatings for optical lens of electronic device (surface coating agent).

Examples of the above-described coatings for car exterior includecoatings for new car, coatings for automobile repair, and coatings forexterior component (aluminum wheel, bumper, or the like).

Examples of the above-described film coatings include coatings foroptical member (optical film, optical sheet, or the like), opticalcoating material, coatings for fiber, coatings for electronic andelectric material, coatings for food packaging, coatings for medicalfilm, coatings for cosmetic packaging, coatings for decorative film, andcoatings for release film.

The polyurethane resin and the polyisocyanate composition describedabove can be used as the coatings and in addition, preferably used inthe fields such as adhesive, ink resin, aqueous resin, thermosettingresin, optical resin (lens or the like), active energy curable resin,and foam resin (flexible foam, rigid foam, or the like).

Examples of the adhesives include adhesives for food packaging,adhesives for household refill packaging, adhesives for electric device,adhesives for liquid crystal display (LCD), adhesives for EL display,adhesives for EL illumination, adhesives for display device (electronicpaper, plasma display, or the like), automobile adhesives, adhesives forhousehold electric appliance, adhesives for solar cell back sheet,adhesives for various cells (lithium ion cell or the like), and moisturecurable adhesives.

Examples of the above-described ink resin include vehicle of various ink(press ink, screen ink, flexographic ink, gravure ink, jet ink, or thelike).

Furthermore, the polyurethane resin can be, for example, widely used ina wide range of fields such as pressure-sensitive adhesive, variousmicrocapsules, plastic lens, artificial and synthetic leather, RIMmolded article, slush powder, elastic molded article (spandex), flexiblegel, robot material, mobility material, health care material, and asubstrate resin of carbon fiber reinforcement plastic (CFRP).

The present invention includes the two-component curable polyurethanecomposition.

The two-component curable polyurethane composition contains apolyisocyanate component that is prepared as a curing agent and a polyolcomponent that is prepared as a base component.

The polyisocyanate component (curing agent) contains the above-describedpolyisocyanate composition, and preferably consists of theabove-described polyisocyanate composition.

The polyisocyanate component (curing agent) can contain theabove-described organic solvent as needed.

When the polyisocyanate component (curing agent) contains the organicsolvent, the content ratio thereof is not particularly limited, andappropriately set in accordance with its purpose and usages.

An example of the polyol component (base component) includes theabove-described polyol component. These polyol components can be usedalone or in combination of two or more. As the polyol component,preferably, high molecular weight polyol is used, more preferably,acrylic polyol is used.

The polyol component (base component) can contain the above-describedorganic solvent as needed.

When the polyol component (base component) contains the organic solvent,the content ratio thereof is not particularly limited, and appropriatelyset in accordance with its purpose and usages.

In the two-component curable polyurethane composition, thepolyisocyanate component (curing agent) and the polyol component (basecomponent) are separately prepared, and used by being blended and mixedat the time of its use.

The mixing ratio of the polyisocyanate component (curing agent) and thepolyol component (base component) is adjusted so that the equivalentratio (OH/NCO) of the hydroxyl group in the polyol component (basecomponent) with respect to the isocyanate group in the polyisocyanatecomponent (curing agent) is, for example, 0.5 or more, preferably 0.75or more, and for example, 2 or less, preferably 1.5 or less.

Also, for example, an additive may be blended into any one or both ofthe polyisocyanate component (curing agent) and the polyol component(base component) as needed. Examples of the additive include epoxyresin, catalysts, coating improvers, leveling agents, defoaming agents,and stabilizers such as antioxidant and ultraviolet absorber. Examplesthereof also include plasticizers, surfactants, pigments (for example,titanium oxide or the like), fillers, organic or inorganic fineparticles, fungicide, and silane coupling agents. The mixing amount ofthe additive is appropriately determined in accordance with its purposeand usages.

The two-component curable polyurethane composition is obtained by usingthe polyisocyanate composition of the present invention, so that it hasexcellent mechanical properties (hardness or the like), designproperties, and durability (chemical resistance, weather resistance, orthe like).

Thus, the two-component curable polyurethane composition is preferablyused in various fields such as coatings (coatings for plastic, coatingsfor car), coating material, adhesive material, pressure-sensitiveadhesive material, ink, and sealant.

The coating material obtained by using the polyisocyanate composition ofthe present invention has excellent mechanical properties (tensilestrength, elongation, adhesive strength, impact resistance, or the like)and durability (chemical resistance, weather resistance, or the like).

Thus, the above-described coating material, among all, is preferablyused as exterior coating and interior coating for car.

EXAMPLES

Next, the present invention is described based on Production Examples,Examples, and Comparative Examples. The present invention is however notlimited by the following Examples. All designations of “part” or “parts”and “%” mean part or parts by mass and % by mass, respectively, unlessotherwise particularly specified in the following description. Thespecific numerical values in mixing ratio (content ratio), propertyvalue, and parameter used in the following description can be replacedwith upper limit values (numerical values defined as “or less” or“below”) or lower limit values (numerical values defined as “or more” or“above”) of corresponding numerical values in mixing ratio (contentratio), property value, and parameter described in the above-described“DESCRIPTION OF EMBODIMENTS”.

Various measurement methods are described in the following.

<Concentration of Isocyanate Monomer (Unit: Mass %)>

The concentration of an unreacted isocyanate monomer (pentamethylenediisocyanate, xylylene diisocyanate) in a polyurethane resin materialwas calculated by the calibration curve obtained from the area value ofthe chromatogram obtained under the following HPLC analysis conditionsby using pentamethylene diisocyanate obtained in Production Example 1 tobe described later, or commercially available xylylene diisocyanate as astandard sample.

Device: Prominence (manufactured by Shimadzu Corporation)

1) Pump LC-20AT

2) Degasser DGU-20A3

3) Auto-sampler SIL-20A

4) Column thermostatic chamber COT-20A

5) Detector SPD-20A

Column: SHISEIDO SILICA SG-120

Column temperature: 40° C.

Eluent: n-hexane/methanol 1,2-dichloroethane=90/5/5 (volume ratio)

Flow rate: 0.2 mL/min

Detection method: UV 225 nm

<Conversion Rate of Isocyanate Group (unit: %)>

The ratio of the area of the peak at the high molecular weight side withrespect to the used isocyanate monomer peak relative to the total peakarea was defined as the conversion rate of the isocyanate group based onthe chromatogram obtained under the following GPC measurementconditions.

Device: HLC-8020 (manufactured by TOSOH CORPORATION)

Column: GI000HXL, G2000HXL, and G3000HXL (hereinabove, manufactured byTOSOH CORPORATION, trade name) connected in series

Column temperature: 40° C.

Eluent: tetrahydrofuran

Flow rate: 0.8 mL/min

Detection method: differential refractive index and UV (wavelength of264 nm) absorption

Standard sample: polyethylene oxide (manufactured by TOSOH CORPORATION,trade name: TSK standard polyethylene oxide)

<Ratio A (unit: %) of Four or More Molecular Product, and Ratio B (unit:%) of Four or More Molecular Product of Xylylene Diisocyanate in Four orMore Molecular Product>

The GPC measurement was performed in the same manner as the measurementof the conversion rate of the isocyanate group after 20 parts by mass ofthe isobutyl benzene was added and dissolved into 80 parts by mass ofthe polyisocyanate composition.

The area ratio (%) of the isobutyl benzene obtained by RI detection wasdefined as I_(RI), the area ratio (%) of the polyisocyanate excludingthe isobutyl benzene was defined as P_(RI), and the area ratio (%) ofthe four or more molecular product was defined as F_(RI). The area ratiocorresponding to the polyethylene oxide-based molecular weight of 600 ormore was defined as the area ratio (%) of the four or more molecularproduct in the RI detection.

The area ratio (%) of the isobutyl benzene obtained by UV detection wasdefined as I_(uv), the area ratio (%) of the polyisocyanate compositionexcluding the isobutyl benzene was defined as P_(uv), and the area ratio(%) of the four or more molecular product was defined as F_(uv). Thearea ratio corresponding to the polyethylene oxide-based molecularweight of 600 or more was defined as the area ratio (%) of the four ormore molecular product in the UV detection.

The ratio A of the four or more molecular product was calculated by thefollowing formula (1).

The ratio B of the four or more molecular product of the xylylenediisocyanate in the four or more molecular product was calculated by thefollowing formula (2).Ratio A (%) of four or more molecular product=F _(RV)% P_(RI)×100  (Formula 1)Ratio B (%) of four or more molecular product of xylylene diisocyanatein four or more molecular product=(F _(UV) ×I _(RI))/(F _(RI) ×I_(UV))×100  (Formula 2)

The ratio of the four or more molecular product in the modified productof the xylylene diisocyanate, the ratio of the four or more molecularproduct in the modified product of the pentamethylene diisocyanate, andthe ratio of the four or more molecular product in the modified productof the hexamethylene diisocyanate were obtained in the same manner asthe above-described formula (1).

<Concentration of Isocyanate Group (Unit: %)>

The concentration of the isocyanate group was measured by using apotentriometric titrator by a toluene/dibutyl amine-hydrochloric acidmethod in conformity with JIS K-1603-1 (2007).

<Concentration of Phosphorus (Unit: Mass %)>

The concentration of the phosphorus was measured by a desk top energydispersive X-ray fluorescence analysis device: Epsilon 3EXL manufacturedby Spectris Co., Ltd.

<Concentration of Hydrolyzable Chlorine of Pentamethylene Diisocyanate(Unit: Ppm)>

The concentration of the hydrolyzable chlorine (HC) was measured inconformity with a test method of the hydrolyzable chlorine described inAnnex 3 of JIS K-1556 (2000).

<Distillation Yield of Isocyanurate Derivative>

The distillation yield of the isocyanurate derivative was obtained bymeasuring the mass of the reaction mixture (liquid before distillation)and that of the isocyanurate derivative (liquid after distillation), andcalculating the ratio of the mass of the isocyanurate derivative withrespect to the mass of the reaction mixture by the following formula.Distillation yield of isocyanurate derivative (mass %)=(mass (g) ofisocyanurate derivative/mass (g) of reaction mixture)×100

<Modification Amount (Alcohol Modification Rate of IsocyanurateDerivative) of Alcohols with Respect to Isocyanurate Derivative>

The modification amount (alcohol modification rate in the reactionmixture) of the alcohols in the reaction mixture was calculated as thecharged mass of the alcohols with respect to the charged mass of thematerial isocyanate monomer (xylylene diisocyanate and/or pentamethylenediisocyanate).

The modification amount (alcohol modification rate of the isocyanuratederivative) of the alcohols with respect to the isocyanurate derivativewas calculated by the following formula.Alcohol Modification Rate (mass %) of Isocyanurate Derivative=(AlcoholModification Rate (mass %) in Reaction Mixture/Distillation Yield (mass%))×100

<Conversion Rate (Reaction Rate) (%)>

The concentration of the isocyanate group in the reaction liquid(reaction mixture or isocyanurate derivative) was measured in conformitywith JIS K-1603-1 (2010), and by obtaining the decreasing rate thereof,the conversion rate (reaction rate) of the isocyanate group wasobtained.

When the isocyanurate derivative was not essentially modified with thealcohols, the conversion rate of the isocyanate group was theisocyanurate conversion rate (trimer conversion rate).

When the isocyanurate derivative of the xylylene diisocyanate wasmodified with the alcohols, the conversion rate of the isocyanate groupafter addition of the alcohols and before addition of the isocyanuratecatalyst was the urethane conversion rate. The conversion rate of theisocyanate group after addition of the isocyanurate-formation catalystwas the isocyanurate conversion rate (trimer conversion rate).

<Analysis of Concentration of Pentamethylene Diisocyanate in ModifiedProduct of Xylylene Diisocyanate and Pentamethylene Diisocyanate>

After the reaction mixture was distilled by the thin-film distillation,the obtained low-boiling point component (unreacted isocyanate monomer)was subjected to GCMS analysis under the following conditions, and theratio of the unreacted monomer in the low-boiling point component wasmeasured.

The ratio of the pentamethylene diisocyanate in the modified product wascalculated from the obtained ratio, the distillation yield, and thecharged ratio of the reaction liquid.

Device: GCMS7980 (Agilent)

Column: Agilent VF-5 ms, 30 m, ϕ 0.25 mm, film thickness 0.25 μm

Oven conditions: column temperature 40° C. (4 min)-10° C./min-250° C. (5min)

Injection temperature: 250° C.

Injection amount: 1 μl (10% dichloromethane solution), split ratio 1/30

He flow: 2.374 ml/min (40° C.)

FID/MSD split ratio=1/2

Production Example 1 (Production of Pentamethylene Diisocyanate (a))

1,5-pentamethylene diisocyanate (hereinafter, may be abbreviated as PDI)(99.9 mass %) was obtained in the same manner as Example 1 in thedescription of the International Patent WO 2012/121291.

To be more specific, 2000 parts by mass of o-dichlorobenzene was chargedinto a jacketed pressure reaction vessel equipped with anelectromagnetic induction stirrer, an automatic pressure control valve,a thermometer, a nitrogen inlet line, a phosgene inlet line, acondenser, and a material feed pump. Next, 2300 parts by mass ofphosgene was added from the phosgene inlet line to start the stirring.Cold water was allowed to pass the jacket of the reaction vessel, andthe internal temperature was kept about 10° C. Then, a solution obtainedby dissolving 400 parts by mass of the pentamethylene diamine (a) in2600 parts by mass of the o-dichlorobenzene was fed with the feed pumpfor 60 minutes, and the cold phosgenation was started at 30° C. or lessunder a normal pressure. After the completion of the feeding, the insideof the pressure reaction vessel became pale brownish white slurry.

Next, a pressure was applied until 0.25 MPa, and furthermore, thermalphosgenation was performed at a pressure of 0.25 MPa at a reactiontemperature of 160° C. for 90 minutes, while the temperature of theinternal liquid in the reaction vessel was gradually increased to 160°C. In the middle of the thermal phosgenation, 1100 parts by mass of thephosgene was further added. In the process of the thermal phosgenation,the internal liquid in the pressure reaction vessel became a palebrownish clear solution. After the completion of the thermalphosgenation, nitrogen gas was allowed to pass at 100 to 140° C. at 100L/hour, and degassing was performed.

Next, after the o-dichlorobenzene was distilled off under a reducedpressure, the pentamethylene diisocyanate was distilled off under thesame reduced pressure, so that 558 parts by mass of the pentamethylenediisocyanate (a₀) having the purity of 98.7% was obtained.

Next, 558 parts by mass of the pentamethylene diisocyanate (a₀) and 0.02parts by mass of tris(tridecyl) phosphite (manufactured by JOHOKUCHEMICAL CO., LTD., trade name: JP-333E) with respect to 100 parts bymass of the pentamethylene diisocyanate were charged into a four-neckflask equipped with a stirrer, a thermometer, a reflux tube, and anitrogen inlet tube to be subjected to heating treatment under a normalpressure at 190° C. for two hours, while the nitrogen was introducedthereto, so that 553 parts by mass of pentamethylene diisocyanate (a₁)having the purity of 98.2% was obtained. The yield of the pentamethylenediisocyanate in the heat treatment was 99.4%.

Next, the pentamethylene diisocyanate (as) after the heat treatment wascharged into a glass-made flask and refined, while being furtherrefluxed, under the conditions of 127 to 132° C. at 2.7 KPa by using arectification device equipped with a distillation column (manufacturedby SHIBATA SCIENTIFIC TECHNOLOGY LTD., trade name: Distilling Column K)equipped with a distillation tube filled with 4 elements of packings(manufactured by Sumitomo Heavy Industries, Ltd., trade name:Sumitomo/Sulzer laboratory packing EX) and a reflux ratio adjustingtimer, and a cooler, so that a fraction having a distillation rate of 20to 80% was collected to obtain pentamethylene diisocyanate (a). Theconcentration of the hydrolyzable chlorine (HC) of the pentamethylenediisocyanate (a) was 70 ppm.

Production Example 2 (Production of Pentamethylene Diisocyanate (b))

Pentamethylene diisocyanate (b) was obtained in the same manner asProduction Example 1, except that a fraction having a distillation rateof 10 to 30% was collected in the refinement. The HC concentration ofthe pentamethylene diisocyanate (b) was 100 ppm.

Production Example 3 (Production of Pentamethylene Diisocyanate (c))

Pentamethylene diisocyanate (c) was obtained in the same manner asProduction Example 1, except that the heat treatment conditions of thepentamethylene diisocyanate (a₀) were changed to 190° C. for 6 hours,and a fraction having a distillation rate of 20 to 80% was collected inthe refinement. The HC concentration of the pentamethylene diisocyanate(c) was 30 ppm.

Production Example 4 (Modified Product A of Pentamethylene Diisocyanate)

The pentamethylene diisocyanate (a) obtained in Production Example 1(500 parts by mass), 1 part by mass of isobutyl alcohol, 0.3 parts bymass of 2,6-di(tert-butyl)-4-methylphenol, and 0.52 parts by mass oftridecyl phosphite (aliphatic organic phosphite, manufactured by JOHOKUCHEMICAL CO., LTD., trade name: JP-310) (hereinafter, the same) werecharged into a four-neck flask equipped with a stirrer, a thermometer, areflux tube, and a nitrogen inlet tube to then react at 80° C. for 2hours. The addition amount of the tridecyl phosphite with respect to thechlorine conversion amount of the hydrolyzable chlorine was 1.1equivalent.

Next, the reaction liquid was cooled to 45° C., and thereafter, 0.05parts by mass ofN-(2-hydroxypropyl)-N,N,N-trimethylammonium-2-ethylhexanoate(manufactured by Air Products and Chemicals, Inc., trade name: DABCO®TMR) as the isocyanurate-formation catalyst was added thereto.

Furthermore, the resulting liquid was allowed to react for 15 minutes,and thereafter, 0.12 parts by mass of the o-toluenesulfonamide was addedthereto at 95° C. The obtained reaction liquid was allowed to pass athin-film distillation device to be distilled at the vacuum of 0.09 KPaand a temperature of 150° C., so that 401 parts by mass of unreactedpentamethylene diisocyanate was obtained.

Furthermore, 0.02 parts by mass of the o-toluenesulfonamide was added to100 parts by mass of the obtained high boiling-side composition(remaining portion after removing the unreacted pentamethylenediisocyanate), so that 100 parts by mass of the modified product A ofthe pentamethylene diisocyanate (isocyanurate derivative ofpentamethylene diisocyanate) was obtained.

In the modified product A of the pentamethylene diisocyanate, theconcentration of the unreacted pentamethylene diisocyanate was below 1mass %, the concentration of the isocyanate group was 25%, and thecontent ratio of the four or more molecular product was 33%.

Production Example 5 (Modified Product B of Pentamethylene Diisocyanate)

A modified product B of the pentamethylene diisocyanate (100 parts bymass) was obtained by the reaction and the distillation treatment underthe same conditions as Production Example 4, except that the mixingratio of the tridecyl phosphite was changed to 0.2 parts by mass andthat of the isocyanurate-formation catalyst(N-(2-hydroxypropyl)-N,N,N-trimethylammonium-2-ethylhexanoate(manufactured by Air Products and Chemicals, Inc., trade name: DABCO®TMR) was changed to 0.1 parts by mass.

The addition amount of the tridecyl phosphite with respect to thechlorine conversion amount of the hydrolyzable chlorine was 0.4equivalent, and the reaction time was 50 minutes.

In the modified product B of the pentamethylene diisocyanate, theconcentration of the unreacted pentamethylene diisocyanate was below 1mass %, the concentration of the isocyanate group was 24.8%, and thecontent ratio of the four or more molecular product was 35%.

Production Example 6 (Modified Product C of Pentamethylene Diisocyanate)

A modified product C of the pentamethylene diisocyanate (100 parts bymass) was obtained by the reaction and the distillation treatment underthe same conditions as Production Example 4, except that thepentamethylene diisocyanate (b) prepared in Production Example 2 wasused, and the mixing ratio of the tridecyl phosphite was changed to 1.55parts by mass.

The addition amount of the tridecyl phosphite with respect to thechlorine conversion amount of the hydrolyzable chlorine was 2.2equivalent, and the reaction time was 10 minutes.

In the modified product C of the pentamethylene diisocyanate, theconcentration of the unreacted pentamethylene diisocyanate was below 1mass %, the concentration of the isocyanate group was 25%, and thecontent ratio of the four or more molecular product was 33%.

Production Example 7 (Modified Product D of Pentamethylene Diisocyanate)

A modified product D of the pentamethylene diisocyanate (100 parts bymass) was obtained by the reaction and the distillation treatment underthe same conditions as Production Example 4, except that thepentamethylene diisocyanate (b) prepared in Production Example 2 wasused, and the mixing ratio of the tridecyl phosphite was changed to 1.27parts by mass.

The addition amount of the tridecyl phosphite with respect to thechlorine conversion amount of the hydrolyzable chlorine was 1.8equivalent, and the reaction time was 12 minutes.

In the modified product D of the pentamethylene diisocyanate, theconcentration of the unreacted pentamethylene diisocyanate was below 1mass %, the concentration of the isocyanate group was 25%, and thecontent ratio of the four or more molecular product was 33%.

Production Example 8 (Modified Product E of Pentamethylene Diisocyanate)

A modified product E of the pentamethylene diisocyanate (100 parts bymass) was obtained by the reaction and the distillation treatment underthe same conditions as Production Example 4, except that thepentamethylene diisocyanate (c) prepared in Production Example 3 wasused, and the mixing ratio of the tridecyl phosphite was changed to 0.22parts by mass.

The addition amount of the tridecyl phosphite with respect to thechlorine conversion amount of the hydrolyzable chlorine was 1.1equivalent, and the reaction time was 13 minutes.

In the modified product E of the pentamethylene diisocyanate, theconcentration of the unreacted pentamethylene diisocyanate was below 1mass %, the concentration of the isocyanate group was 25%, and thecontent ratio of the four or more molecular product was 33%.

Production Example 9 (Modified Product F of Pentamethylene Diisocyanate)

The pentamethylene diisocyanate (a) obtained in Production Example 1(500 parts by mass), 1 part by mass of isobutyl alcohol, 0.3 parts bymass of 2,6-di(tert-butyl)-4-methylphenol, and 0.52 parts by mass oftridecyl phosphite were charged into a four-neck flask equipped with astirrer, a thermometer, a reflux tube, and a nitrogen inlet tube to thenreact at 80° C. for 2 hours. The addition amount of the tridecylphosphite with respect to the chlorine conversion amount of thehydrolyzable chlorine was 1.1 equivalent.

Next, the reaction liquid was cooled to 70° C., and thereafter, 0.03parts by mass ofN-(2-hydroxypropyl)-N,N,N-trimethylammonium-2-ethylhexanoate(manufactured by Air Products and Chemicals, Inc., trade name: DABCO®TMR) as the isocyanurate-formation catalyst was added thereto.

Furthermore, the resulting liquid was allowed to react at 80° C. for 120minutes, and thereafter, 0.1 parts by mass of the o-toluenesulfonamidewas added thereto. The obtained reaction liquid was allowed to pass athin-film distillation device to be distilled at the vacuum of 0.09 KPaand a temperature of 150° C., so that 300 parts by mass of unreactedpentamethylene diisocyanate was obtained.

Furthermore, 0.04 parts by mass of the o-toluenesulfonamide was added to200 parts by mass of the obtained high boiling-side composition, so thatthe modified product F of the pentamethylene diisocyanate was obtained.

In the modified product F of the pentamethylene diisocyanate, theconcentration of the unreacted pentamethylene diisocyanate was below 1mass %, the concentration of the isocyanate group was 23.3%, and thecontent ratio of the four or more molecular product was 60%.

Production Example 10 (Modified Product G of PentamethyleneDiisocyanate)

The pentamethylene diisocyanate (a) obtained in Production Example 1(500 parts by mass), 22.3 parts by mass of trimethylolpropane, 0.3 partsby mass of 2,6-di(tert-butyl)-4-methylphenol, and 0.52 parts by mass oftridecyl phosphite were charged into a four-neck flask equipped with astirrer, a thermometer, a reflux tube, and a nitrogen inlet tube to thenreact at 80° C. for 2 hours. The addition amount of the tridecylphosphite with respect to the chlorine conversion amount of thehydrolyzable chlorine was 1.1 equivalent.

Next, the reaction liquid was cooled to 70° C., and thereafter, 0.03parts by mass ofN-(2-hydroxypropyl)-N,N,N-trimethylammonium-2-ethylhexanoate(manufactured by Air Products and Chemicals, Inc., trade name: DABCO®TMR) as the isocyanurate-formation catalyst was added thereto.

Furthermore, the resulting liquid was allowed to react at 80° C. for 60minutes, and thereafter, 0.1 parts by mass of the o-toluenesulfonamidewas added thereto. The obtained reaction liquid was allowed to pass athin-film distillation device to be distilled at the vacuum of 0.09 KPaand a temperature of 150° C., so that 300 parts by mass of unreactedpentamethylene diisocyanate was obtained.

Furthermore, 0.06 parts by mass of the o-toluenesulfonamide was added to300 parts by mass of the obtained high boiling-side composition, so thatthe modified product G of the pentamethylene diisocyanate was obtained.

In the modified product G of the pentamethylene diisocyanate, theconcentration of the unreacted pentamethylene diisocyanate was below 1mass %, the concentration of the isocyanate group was 20.7%, and thecontent ratio of the four or more molecular product was 70%.

Production Example 11 (Modified Product H of Xylylene Diisocyanate)

Under a nitrogen atmosphere, 100 parts by mass of 1,3-xylylenediisocyanate (manufactured by Mitsui Chemicals, Inc., m-XDI), 0.025 phrof 2,6-di(tert-butyl)-4-methylphenol (also known as:dibutylhydroxytoluene, BHT, hindered phenol antioxidant), and 0.05 phrof tetraphenyl-dipropyleneglycol-diphosphite (JPP-100 (trade name,manufactured by JOHOKU CHEMICAL CO., LTD.), organic phosphite, auxiliarycatalyst) were charged into a reaction vessel equipped with athermometer, a stirrer, a nitrogen inlet tube, and a cooling tube, andthereafter, 1.96 parts by mass of 1,3-butanediol was added to theobtained charged liquid. The temperature of the charged liquid wasincreased to 75° C. to be subjected to urethane-formation reaction. Theequivalent ratio (NCO/OH) of the isocyanate group of the1,3-xylylenediisocyanate with respect to the hydroxy group of the1,3-butanediol was 24.

Next, the resulting product was allowed to react at the same temperaturefor 120 minutes, and the temperature thereof was decreased to 60° C.Then, as the isocyanurate-formation catalyst, 0.064 phr (solid contentconversion of 0.024 phr) of the solution (37% methanol solution) of thehydroxide of the tetrabutylammonium (TBAOH) was blended thereto to besubjected to isocyanurate-formation reaction. The isocyanurate-formationreaction was stopped in 190 minutes after the start of the reaction. Themaximum achieving temperature during the reaction was 63° C.

The obtained reaction mixture was allowed to pass a thin-filmdistillation device (temperature of 150° C., vacuum of 50 Pa), and theunreacted xylylene diisocyanate was removed, so that the modifiedproduct (isocyanurate derivative of the xylylene diisocyanate) H of thexylylene diisocyanate was obtained. The distillation yield was 44.7 mass%.

In the isocyanurate derivative (after distillation), the alcoholmodification rate in the reaction was 4.38 mass %, the conversion rateof the isocyanate group was 24.7 mass %, and the content ratio of thefour or more molecular product was 50%.

Production Examples 12 to 15 (Modified Products I to L of XylyleneDiisocyanate)

Modified products I to L of the xylylene diisocyanate were obtained inthe same manner as Production Example 11, except that the conditionswere changed to those shown in Table 2. The distillation yield, thealcohol modification rate, the conversion rate of the isocyanate group,and the content ratio of the four or more molecular product inProduction Examples were shown in Table 2.

Production Example 16 (Modified Product M of Xylylene Diisocyanate andPentamethylene Diisocyanate)

Under a nitrogen atmosphere, 60 parts by mass of 1,3-xylylenediisocyanate (manufactured by Mitsui Chemicals. Inc., m-XDI), 440 partsby mass of the pentamethylene diisocyanate (a) obtained in ProductionExample 1, 0.025 phr of 2,6-di(tert-butyl)-4-methylphenol (also knownas: dibutylhydroxytoluene, BHT, hindered phenol antioxidant), and 0.05phr of tetraphenyl-dipropyleneglycol-diphosphite (JPP-100 (trade name,manufactured by JOHOKU CHEMICAL CO., LTD.), organic phosphite, auxiliarycatalyst) were charged into a reaction vessel equipped with athermometer, a stirrer, a nitrogen inlet tube, and a cooling tube. Thetemperature of the charged liquid was increased to 75° C.

Then, as the isocyanurate-formation catalyst, 0.338 parts by mass (solidcontent conversion of 0.125 parts by mass) of the solution (37% methanolsolution) of the hydroxide of the tetrabutylammonium (TBAOH) was blendedthereto to be subjected to isocyanurate-formation reaction. Theisocyanurate-formation reaction was stopped in 400 minutes after thestart of the reaction. The maximum achieving temperature during thereaction was 79° C.

The obtained reaction mixture was allowed to pass a thin-filmdistillation device (temperature of 150° C., vacuum of 50 Pa), and theunreacted xylylene diisocyanate and the unreacted pentamethylenediisocyanate were removed, so that the modified product (isocyanuratederivative of the xylylene diisocyanate and the pentamethylenediisocyanate) M of the xylylene diisocyanate and the pentamethylenediisocyanate was obtained. The distillation yield was 44.8 mass %.

The conversion rate of the isocyanate group in the reaction was 25.2mass %, and the content ratio of the four or more molecular product was49%.

In the obtained modified product M, the ratio of the pentamethylenediisocyanate with respect to the total amount of the xylylenediisocyanate and the pentamethylene diisocyanate was 77 mol %.

Production Example 17 (Modified Product N of Xylylene Diisocyanate andPentamethylene Diisocyanate)

Under a nitrogen atmosphere, 30 parts by mass of 1,3-xylylenediisocyanate (manufactured by Mitsui Chemicals, Inc., m-XDI), 470 partsby mass of the pentamethylene diisocyanate (a) obtained in ProductionExample 1, 6.4 parts by mass of isobutyl alcohol, 0.025 phr of2,6-di(tert-butyl)-4-methylphenol (also known as: dibutylhydroxytoluene,BHT, hindered phenol antioxidant), and 0.05 parts by mass oftetraphenyl.dipropyleneglycol.diphosphite (JPP-100 (trade name,manufactured by JOHOKU CHEMICAL CO., LTD.), organic phosphite, auxiliarycatalyst) were charged into a reaction vessel equipped with athermometer, a stirrer, a nitrogen inlet tube, and a cooling tube. Thetemperature of the charged liquid was increased to 75° C. to besubjected to urethane-formation reaction. The equivalent ratio (NCO/OH)of the isocyanate group of the 1,3-xylylenediisocyanate and thepentamethylene diisocyanate with respect to the hydroxy group of theisobutyl alcohol was 75.

Then, as the isocyanurate-formation catalyst, 0.013 parts by mass (solidcontent conversion of 0.005 parts by mass) of the solution (37% methanolsolution) of the hydroxide of the tetrabutylammonium (TBAOH) was blendedthereto to be subjected to isocyanurate-formation reaction. Theisocyanurate-formation reaction was stopped in 300 minutes after thestart of the reaction. The maximum achieving temperature during thereaction was 78° C.

The obtained reaction mixture was allowed to pass a thin-filmdistillation device (temperature of 150° C., vacuum of 50 Pa), and theunreacted xylylene diisocyanate and the unreacted pentamethylenediisocyanate were removed, so that the modified product N of thexylylene diisocyanate and the pentamethylene diisocyanate was obtained.The distillation yield was 28.2 mass %.

The conversion rate of the isocyanate group in the reaction was 17.2mass %, and the content ratio of the four or more molecular product was42%.

In the obtained modified product N, the ratio of the pentamethylenediisocyanate with respect to the total amount of the xylylenediisocyanate and the pentamethylene diisocyanate was 83%.

Examples 1 to 29 and Comparative Examples 1 to 4 (Preparation ofPolyisocyanate Composition and Polyurethane Resin)

Each of the modified products of the pentamethylene diisocyanateobtained in Production Examples or a commercially available TakenateD-170N (isocyanurate derivative of hexamethylene diisocyanate,manufactured by Mitsui Chemicals, Inc.), and each of the modifiedproducts of the xylylene diisocyanate obtained in Production Examples ora commercially available Takenate D-110N (trimethylol propane modifiedproduct of the xylylene diisocyanate, manufactured by Mitsui Chemicals,Inc.) were blended at the ratio described in Tables 3 to 7, so thatpolyisocyanate compositions were prepared.

In tables, the mixing ratio of the above-described components was shownas the ratio of the material isocyanate monomer (xylylene diisocyanate,pentamethylene diisocyanate, and/or hexamethylene diisocyanate).

The modified product of the xylylene diisocyanate and the pentamethylenediisocyanate was used as the polyisocyanate composition.

The polyisocyanate composition was diluted with ethyl acetate, and asolution of the solid content of 75 mass % was prepared. Next, theobtained solution of the polyisocyanate composition and acrylic polyol(manufactured by Mitsui Chemicals, Inc., OLESTAR Q-417-5, hydroxyl valueof 56.1 mgKOH/g, solid content concentration of 60%, diluent solvent:butyl acetate) were blended so that the equivalent ratio (NCO/OH) of theisocyanate group in the polyisocyanate composition with respect to thehydroxyl group in the acrylic polyol was 1.0.

Next, butyl acetate was added so that the viscosity of the mixed liquidwas 30 to 50 mPa·s. Thereafter, DBTDL (dibutyltin dilaurate (IV)(manufactured by Wako Pure Chemical Industries, Ltd.)) as the catalystwas blended so as to have 300 ppm with respect to the solid content ofthe acrylic polyol to be then stirred at 23° C. for 90 seconds.

Next, the mixed liquid was applied to a standard test plate (type:electrolytic zinc-plated steel plate and glass plate (hereinafter,abbreviated as test plate) in conformity with JIS G 3313 (2010) to bethen allowed to cure at 80° C. for 30 minutes, so that a coated film ofthe polyurethane resin having a thickness of about 35 μm was obtained.

The obtained polyurethane resin was left to stand at 23° C. indoors atrelative humidity of 55% for seven days.

<Evaluation>

<Smoothness (Design Properties)>

The smoothness in Long Wave mode was evaluated with Wave-scan dualmanufactured by BYK-Gardner

<Transparency (Appearance)>

The coated film applied onto the glass substrate was visually evaluated.

The reference of the evaluation was described in the following.

5 Transparent

4 Barely cloudy

3 Slightly cloudy (more cloudy than 4)

2 Cloudy (more cloudy than 3)

1 Quite cloudy (more cloudy than 2)

<Koenig Pendulum Hardness (Unit: Number of Times)>

By using a pendulum durometer manufactured by BYK Japan KK, the Koenigpendulum hardness of the coated film was measured in conformity withASTM D 4366 (2014). Two patterns of 30 minutes after curing and 24 hoursafter curing were measured.

<Weather Resistance Test>

QUV test was performed under the following conditions. The E value ofthe coated film before or after the test was measured with aspectroscopic colorimeter (manufactured by NIPPON DENSHOKU INDUSTRIESCo., LTD.). A difference (ΔE) of the E value before and after theapplication of ultraviolet rays was calculated, and the degree ofdiscoloration of the coated film was evaluated.

Also, a relationship of the mole ratio of the pentamethylenediisocyanate modified product with AE was confirmed from the formulation(Examples 4 to 8 and Comparative Examples 1 to 2) using the modifiedproduct A of the pentamethylene diisocyanate and the modified product Iof the xylylene diisocyanate. The results are shown in FIG. 1.

QUV test condition device: Dewpanel light control weather meter (type:FDP), manufactured by Suga Test Instruments Co., Ltd.)

Cycle conditions: Application: Irradiance: 28 W/m²

60° C.×10% RH×four hours→darkening: 50° C.×95% RH×four hours

Application time: 240 hours

<Chemical Resistance (Unit: Times)>

A swab sufficiently impregnated with a test liquid was put on the coatedfilm in tight contact with the test plate to make a round trip in adistance of about 1 cm with applying a constant load thereto. Theoperation was repeated, and when damage was observed in the coated film,the test was stopped.

The round trip was counted as once, and the number of times until damagewas observed in the coated film was defined as the chemical resistance.Methyl ethyl ketone was used as the test liquid.

TABLE 1 No. Production Production Production Production ProductionProduction Production Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10Modified Product of PDI A B C D E F G PDI Type a a b b c a a MixingAmount parts by mass 500 500 500 500 500 500 500 HC ppm 70 70 100 100 3070 70 Additive BHT parts by mass 0.3 0.3 0.3 0.3 0.3 0.3 0.3 JP-310parts by mass 0.52 0.2 1.55 1.27 0.22 0.52 0.52 equivalent ratio 1.1 0.42.2 1.8 1.1 1.1 1.1 to HC (chlorine) Alcohols Type iBA iBA iBA iBA iBAiBA TMP Catalyst Type DABCO- DABCO- DABCO- DABCO- DABCO- DABCO- DABCO-TMR TMR TMR TMR TMR TMR TMR Mixing Amount parts by mass 0.05 0.1 0.050.05 0.05 0.03 0.03 Reaction Reaction Start Temperature ° C. 45 45 45 4545 70 70 Conditions Reaction Stop Temperature ° C. 95 95 95 95 95 80 80Reaction Time minutes 15 50 10 12 13 90 60 Terminator OTS parts by mass0.05 0.1 0.05 0.05 0.05 0.04 0.04 Properties Concentration of IsocyanateGroup mass % 25.0 24.8 25.0 25.0 25.0 23.8 20.7 Ratio of Four or moremass % 33 35 33 33 33 60 70 Molecular Product Content of Phosphite ppm1041 397 3116 2549 446 1041 1041

TABLE 2 No. Production Production Production Production Production Ex.11 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Modified Product of XDI H I J K L Mixingof Alcohol Modifier Type 1,3-BG 1,3-BG 1,3-BG 1,3-BG 1,3-BG ReactionLiquid parts by mass 1.96 1.96 0.5 0.5 0.5 Urethane-Formation R[NCO]/[OH] 24 24 96 96 96 Reaction Conditions Reaction Temperature ° C.75 75 75 75 75 Reaction Time minutes 120 120 120 120 120 Isocyanurate-Catalyst Type TBAOH TBAOH TBAOH TBAOH TBAOH Formation Reaction AdditionAmount in Solid 0.024 0.015 0.018 0.018 0.018 Conditions ContentConversion (phr) Reaction Start Temperature ° C. 60 60 60 60 60 MaximumAchieving Temperature ° C. 63 71 65 65 65 Reaction Time minutes 190 390120 110 200 Concentration of Isocyanate Group after mass % 33.0 28.837.0 37.2 36.0 Isocyanurate-Formation Reaction Conversion Rate ofIsocyanate Group % 24.66 34.25 16.40 15.84 18.55 Isocyanurate ConversionRate % 18.9 28.8 15.7 15.2 17.6 Distillation Yield % 45 60 29 28 33Alcohol Modification Rate mass % 4.36 3.27 1.72 1.79 1.52 Ratio of Fouror More mass % 50 60 30 28 36 Molecular Product

TABLE 3 No. Production Production Ex. 16 Ex. 17 Modified Product ofXDI•PDI M N Mixing of PDI mol % 90 95 Reaction XDI mol % 10 5 LiquidMixing Amount parts by mass 500 500 of PDI + XDI Alcohol Modifier Type —iBA parts by mass — 6.4 Alcohol Modification — 1.25 Amount (mass %)Urethane-Formation R [NCO]/[OH] — 75 Reaction Reaction Temperature ° C.— 75 Conditions Reaction Time minutes — 120 Isocyanurate- Catalyst TypeTBAOH TBAOH Formation Addition Amount 0.005 0.005 Reaction in SolidContent Conditions Conversion (phr) Reaction Start ° C. 75 75Temperature Maximum Achieving ° C. 79 78 Temperature Reaction Timeminutes 400 300 Concentration of mass % 53.8 53.8 Isocyanate Group atTime of Start of Reaction Concentration of mass % 53.8 52.5 IsocyanateGroup after Urethane-Formation Reaction Concentration of mass % 40.344.6 Isocyanate Group after Isocyanurate-Formation Reaction ConversionRate % 25.2 17.2 of Isocyanate Group Urethane % 0.0 2.4 Conversion RateIsocyanurate % 25.2 14.8 Conversion Rate Distillation Yield % 44.8 28.2Alcohol Modification Rate mass % — 4.43 Ratio of Four mass % 49 42 orMore Molecular Product PDI in Modified mol % 77 83 Product of XDI•PDI

TABLE 4 No. Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8Polyisocyanate PDI Modified Product Isocyanurate Derivative Type A A A AA A A A Composition mol % 90 80 65 93 90 80 70 65 Concentration of ppm125 125 125 125 125 125 125 125 Phosphorus Ratio of Four or More mass %33 33 33 33 33 33 33 33 Molecular Product XDI Modified ProductIsocyanurate Derivative Type H H H I I I I I mol % 10 20 35 7 10 20 3035 Concentration of ppm 110 110 110 70 70 70 70 70 Phosphorus Ratio ofFour or More mass % 36 36 36 50 50 50 50 50 Molecular Product PolyolDerivative mol % — — — — — — — — Ratio of Four or More mass % — — — — —— — — Molecular Product Modified Product of XDI · PDI Type — — — — — — —— Concentration of Phosphorus ppm 124 122 120 121 120 114 109 106 Ratioof Four or More Molecular mass % 33.3 33.6 34.1 34.2 34.7 36.4 38.1 39.0Product (Total Amount) Ratio of XDI Four or More Molecular Product mass% 10.8 21.4 37.0 10.2 14.4 27.5 39.4 44.9 in Four or More MolecularProduct Hue APHA 50 50 60 50 50 50 50 60 Properties of Smoothness (Lw)21.9 23.9 25 21 22.2 24.5 26 26.8 Coated Film Appearance Transparency 55 5 5 5 5 5 5 Curing Properties Pendulum Hardness 30 minutes afterCuring 47 51 55 48 51 55 58 62 24 hours after Curing 88 90 100 86 91 95100 106 Light Resistance (Weather Resistance) ΔE 1.5 1.8 3.5 1.5 1.6 1.82.8 3.4 Chemical Resistance MEK Rubbing Number of Times 220 250 300 230250 280 300 320

TABLE 5 No. Ex. 9 Ex. 10 Ex. 11 Ex. 12 Polyisocyanate PDI ModifiedProduct Isocyanurate Derivative Type B C D E Composition mol % 80 80 8070 Concentration of Phosphorus ppm 60 350 125 125 Ratio of Four or MoreMolecular Product mass % 33 33 33 33 XDI Modified Product IsocyanurateDerivative Type I I I I mol % 20 20 20 30 Concentration of Phosphorusppm 70 70 70 70 Ratio of Four or More Molecular Product mass % 50 50 5050 Polyol Modified Product mol % — — — — Ratio of Four or More MolecularProduct mass % — — — — Modified Product of XDI · PDI Type — — — —Concentration of Phosphorus ppm 62 294 114 109 Ratio of Four or MoreMolecular Product (Total Amount) mass % 36.4 36.4 36.4 38.1 Ratio of XDIFour or More Molecular Product in Four or More mass % 27.5 27.5 27.539.4 Molecular Product Hue APHA 100 50 50 60 Properties of Smoothness(Lw) 26.2 24.3 24.7 25.1 Coated Film Appearance Transparency 5 4 4 5Curing Properties Pendulum Hardness 30 minutes after Curing 53 55 54 5824 hours after Curing 94 95 95 99 Light Resistance (Weather Resistance)ΔE 2.8 2.1 2 2.2 Chemical Resistance MEK Rubbing Number of Times 260 280280 300 No. Ex. 13 Ex. 14 Ex. 15 Ex. 16 Polyisocyanate PDI ModifiedProduct Isocyanurate Derivative Type F F F G Composition mol % 90 80 7090 Concentration of Phosphorus ppm 60 60 60 30 Ratio of Four or MoreMolecular Product mass % 60 60 60 70 XDI Modified Product IsocyanurateDerivative Type I I I J mol % 10 20 30 10 Concentration of Phosphorusppm 70 70 70 70 Ratio of Four or More Molecular Product mass % 50 50 5050 Polyol Modified Product mol % — — — — Ratio of Four or More MolecularProduct mass % — — — — Modified Product of XDI · PDI Type — — — —Concentration of Phosphorus ppm 61 62 63 34 Ratio of Four or MoreMolecular Product (Total Amount) mass % 59.0 58.0 57.0 68.0 Ratio of XDIFour or More Molecular Product in Four or More mass % 8.5 17.2 26.3 7.4Molecular Product Hue APHA 50 50 50 50 Properties of Smoothness (Lw)23.7 24.9 26.6 24.5 Coated Film Appearance Transparency 4 4 4 4 CuringProperties Pendulum Hardness 30 minutes after Curing 54 58 62 56 24hours after Curing 97 102 106 98 Light Resistance (Weather Resistance)ΔE 1.7 1.9 2.9 1.6 Chemical Resistance MEK Rubbing Number of Times 280320 350 290

TABLE 6 No. Ex. 17 Ex. 18 Ex. 19 Ex. 20 Polyisocyanate PDI ModifiedProduct Isocyanurate Derivative Type G A A A Composition mol % 65 93 8065 Concentration of Phosphorus ppm 30 125 125 125 Ratio of Four or MoreMolecular Product mass % 70 33 33 33 XDI Modified Product IsocyanurateDerivative Type J J J J mol % 35 7 20 35 Concentration of Phosphorus ppm70 50 50 50 Ratio of Four or More Molecular Product mass % 50 60 60 60Polyol Modified Product mol % — — — — Ratio of Four or More MolecularProduct mass % — — — — Modified Product of XDI · PDI Type — — — —Concentration of Phosphorus ppm 44 120 110 99 Ratio of Four or MoreMolecular Product (Total Amount) mass % 63.0 34.9 38.4 42.5 Ratio of XDIFour or More Molecular Product in Four or More mass % 27.8 12.0 31.349.5 Molecular Product Hue APHA 50 50 50 50 Properties of Smoothness(Lw) 27.4 21.7 25.2 27.8 Coated Film Appearance Transparency 4 5 5 4Curing Properties Pendulum Hardness 30 minutes after Curing 65 50 57 6524 hours after Curing 110 90 101 110 Light Resistance (WeatherResistance) ΔE 3.3 1.6 2.1 3.6 Chemical Resistance MEK Rubbing Number ofTimes 390 240 300 350 No. Ex. 21 Ex. 22 Ex. 23 Ex. 24 Polyisocyanate PDIModified Product Isocyanurate Derivative Type F F F A Composition mol %93 80 65 80 Concentration of Phosphorus ppm 60 60 60 125 Ratio of Fouror More Molecular Product mass % 60 60 60 33 XDI Modified ProductIsocyanurate Derivative Type K K K L mol % 7 20 35 20 Concentration ofPhosphorus ppm 130 130 130 130 Ratio of Four or More Molecular Productmass % 30 30 30 28 Polyol Modified Product mol % — — — — Ratio of Fouror More Molecular Product mass % — — — — Modified Product of XDI · PDIType — — — — Concentration of Phosphorus ppm 65 74 85 126 Ratio of Fouror More Molecular Product (Total Amount) mass % 57.9 54.0 49.5 32.0Ratio of XDI Four or More Molecular Product in Four or More mass % 3.611.1 21.2 17.5 Molecular Product Hue APHA 50 50 50 50 Properties ofSmoothness (Lw) 22 23.4 24.8 23 Coated Film Appearance Transparency 5 55 5 Curing Properties Pendulum Hardness 30 minutes after Curing 47 53 5945 24 hours after Curing 86 95 99 82 Light Resistance (WeatherResistance) ΔE 1.5 2 5.8 2.2 Chemical Resistance MEK Rubbing Number ofTimes 230 260 300 250

TABLE 7 No. Ex. 25 Ex. 26 Ex. 27 Ex. 28 Ex. 29 Polyisocyanate PDIModified Product Isocyanurate Derivative Type A A A — — Composition orHDI Modified mol % 90 80 65 — — Product Concentration of Phosphorus ppm125 125 125 — — Ratio of Four or More mass % 33 33 33 — — MolecularProduct XDI Modified Product Isocyanurate Derivative Type — — — — — mol% — — — — — Concentration of Phosphorus ppm — — — — — Ratio of Four orMore mass % — — — — — Molecular Product Polyol Modified Product TypeD-110N D-110N D-110N — — mol % 10 20 35 — — Ratio of Four or More mass %40 40 40 — — Molecular Product Modified Product of XDI · PDI Type — — —M N Concentration or Phosphorus ppm 113 100 81 — — Ratio of Four or MoreMolecular mass % 29.7 26.4 21.5 49 42 Product (Total Amount) Ratio ofXDI Four or More Molecular mass % 11.9 23.3 39.5 — — Products Four orMore Molecular Product Hue APHA 50 50 60 60 60 Properties of Smoothness(Lw) 22 24.1 25.8 24.3 23.8 Coated Film Appearance Transparency 5 5 5 55 Curing Properties Pendulum Hardness 30 minutes after Curing 47 51 5663 60 24 hours after Curing 85 90 98 105 101 Light Resistance (WeatherResistance) ΔE 3.2 5.3 9.2 2.3 1.8 Chemical Resistance MEK RubbingNumber of Times 210 220 230 370 340 No. Comp. Comp. Ex. 1 Comp. Ex. 2Comp. Ex. 3 Ex. 4 Polyisocyanate PDI Modified Product IsocyanurateDerivative Type A A A D-170N Composition or HDI Modified mol % 97 50 5080 Product Concentration of Phosphorus ppm 125 125 125 — Ratio of Fouror More mass % 33 33 33 58 Molecular Product XDI Modified ProductIsocyanurate Derivative Type I I — — mol % 3 50 — — Concentration ofPhosphorus ppm 70 70 — — Ratio of Four or More mass % 50 50 — —Molecular Product Polyol Modified Product Type — — D-110N D-110N mol % —— 50 20 Ratio of Four or More mass % — — 40 40 Molecular ProductModified Product of XDI · PDI Type — — — — Concentration or Phosphorusppm 123 98 63 63 Ratio of Four or More Molecular mass % 33.5 41.5 16.554.4 Product (Total Amount) Ratio of XDI Four or More Molecular mass %4.5 60.2 54.8 14.7 Products Four or More Molecular Product Hue APHA 5070 60 60 Properties of Smoothness (Lw) 20.2 29.8 27.2 28.5 Coated FilmAppearance Transparency 5 3 5 5 Curing Properties Pendulum Hardness 30minutes after Curing 43 65 59 55 24 hours after Curing 80 110 100 98Light Resistance (Weather Resistance) ΔE 1.5 6.2 16.9 18 ChemicalResistance MEK Rubbing Number of Times 200 330 260 240

The details of the abbreviations in Tables are shown in the following.

PDI: pentamethylene diisocyanate

XDI: xylylene diisocyanate

HC: hydrolyzable chlorine

BHT: 2,6-di(tert-butyl)-4-methylphenol (hindered phenol antioxidant)

JP-310: tridecyl phosphite (organic phosphite, manufactured by JOHOKUCHEMICAL CO., LTD., trade name)

OTS: o-toluenesulfonamide

D-110N: Takenate D-110N, trimethylol propane modified product ofxylylene diisocyanate, content of NCO group: 11.5 mass %, solid contentconcentration: 75 mass %, solvent: ethyl acetate, viscosity (25° C.):500 mPa·s, manufactured by Mitsui Chemicals, Inc.

D-170N: Takenate D-170N, isocyanurate derivative of hexamethylenediisocyanate, content of NCO group: 20.7 mass %, solid contentconcentration: 100 mass %, viscosity (25° C.): 2000 mPa·s, manufacturedby Mitsui Chemicals, Inc.

While the illustrative embodiments of the present invention are providedin the above description, such is for illustrative purpose only and itis not to be construed as limiting the scope of the present invention.Modification and variation of the present invention that will be obviousto those skilled in the art is to be covered by the following claims.

INDUSTRIAL APPLICABILITY

The polyisocyanate composition and the polyurethane resin of the presentinvention are widely used in various fileds such as coatings, adhesivesfor industrial purposes, adhesives for packing, hot melt adhesives,pressure-sensitive adhesives, overprint varnish (OP varnish), ink,sealant, and binder resins.

The invention claimed is:
 1. A polyisocyanate composition containing: amodified product of xylylene diisocyanate and a modified product ofpentamethylene diisocyanate, and/or a modified product of the xylylenediisocyanate and the pentamethylene diisocyanate, and the ratio of thepentamethylene diisocyanate with respect to the total amount of thexylylene diisocyanate and the pentamethylene diisocyanate is 60 mol % ormore and 95 mol % or less, wherein the modified product is a multiplemolecular product containing two or more molecules of the xylylenediisocyanate and/or the pentamethylene diisocyanate, and the contentratio of the multiple molecular product containing four or moremolecules of the xylylene diisocyanate and/or the pentamethylenediisocyanate with respect to the total amount of the polyisocyanatecomposition is 30 mass % or more and 65 mass % or less.
 2. Thepolyisocyanate composition according to claim 1, wherein the multiplemolecular product containing four or more molecules of the xylylenediisocyanate and/or the pentamethylene diisocyanate contains a multiplemolecular product containing four or more molecules of the xylylenediisocyanate, and the content ratio of the multiple molecular productcontaining four or more molecules of the xylylene diisocyanate withrespect to the total amount of the multiple molecular product containingfour or more molecules of the xylylene diisocyanate and/or thepentamethylene diisocyanate is 5 mass % or more and 45 mass % or less.3. The polyisocyanate composition according to claim 1, wherein themodified product contains at least one functional group selected fromthe group consisting of the following (a) to (i): (a) isocyanurategroup, (b) allophanate group, (c) biuret group, (d) urethane group, (e)urea group, (f) uretdione group, (g) iminooxadiazinedione group, (h)uretonimine group, and (i) carbodiimide group.
 4. A polyurethane resinobtained from reaction of the polyisocyanate composition according toclaim 1 with an active hydrogen group-containing compound.
 5. Atwo-component curable polyurethane composition containing apolyisocyanate component containing the polyisocyanate compositionaccording to claim 1, and a polyol component.
 6. A coating materialobtained from the two-component curable polyurethane compositionaccording to claim 5.